WO2021004492A1 - 基于硅和锗的scm-25分子筛、其制备方法及其用途 - Google Patents

基于硅和锗的scm-25分子筛、其制备方法及其用途 Download PDF

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WO2021004492A1
WO2021004492A1 PCT/CN2020/100969 CN2020100969W WO2021004492A1 WO 2021004492 A1 WO2021004492 A1 WO 2021004492A1 CN 2020100969 W CN2020100969 W CN 2020100969W WO 2021004492 A1 WO2021004492 A1 WO 2021004492A1
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molecular sieve
source
ray diffraction
germanium
following table
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French (fr)
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杨为民
付文华
袁志庆
王振东
滕加伟
陶伟川
赵胜利
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to US17/626,077 priority Critical patent/US11952283B2/en
Priority to JP2022501273A priority patent/JP7624430B2/ja
Priority to KR1020227004483A priority patent/KR102880813B1/ko
Priority to EP20836468.7A priority patent/EP3998232A4/en
Priority to BR112022000316A priority patent/BR112022000316A2/pt
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

  • the invention relates to a SCM-25 molecular sieve, its synthesis method and its use.
  • molecular sieves are a kind of porous crystalline material. So far, 245 kinds of molecular sieves with known structures have been discovered, and molecular sieves with new structures are constantly emerging. Due to the regular molecular size pore structure, strong acidity and high hydrothermal stability, molecular sieves are widely used in the fields of catalysis, adsorption and ion exchange, and they play an irreplaceable role.
  • the framework of molecular sieve is usually formed by coordinating tetrahedrons (TO 4 ) connected by common vertices (usually oxygen atoms). For molecular sieves, the tetrahedrons in the framework are mainly SiO 4 tetrahedra and AlO 4 tetrahedra.
  • These two tetrahedra can be replaced by other tetrahedra to form molecular sieves or molecular sieves with different framework structures.
  • AlO 4 tetrahedron can be replaced by GaO 4 or ZnO 4 tetrahedron to form the framework of heteroatom molecular sieve together with SiO 4 tetrahedron.
  • Ge and Si have similar coordination properties, and can also form tetrahedral coordination structure. , Through the connection of GeO 4 and SiO 4 , a large number of new germanium-containing molecular sieves or molecular sieve-like structures can be formed.
  • the invention provides a molecular sieve based on silicon and germanium and a method for synthesizing the molecular sieve.
  • the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
  • the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
  • the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
  • the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
  • the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5; 0.05 ⁇ k ⁇ 1.0, preferably 0.05 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.4;
  • Q is an organic template, 0.01 ⁇ m ⁇ 1.0, preferably 0.02 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.3;
  • the organic template is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-tetramethylpiperidine
  • R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
  • X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -); 0.005 ⁇ p ⁇ 0.5, preferably 0.01 ⁇ p ⁇ 0.4, more preferably 0.01 ⁇ p ⁇ 0.3, more preferably 0.02 ⁇ p ⁇ 0.2.
  • a method for preparing a molecular sieve based on silicon and germanium comprising forming a silicon source, a germanium source, a fluorine source, an organic template Q and water or a silicon source, a germanium source, a fluorine source, an organic template Q and water The step of crystallizing the mixture of, to obtain the molecular sieve; and optionally, the step of calcining the obtained molecular sieve;
  • the organic template Q is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-tetramethylpiperidine hydrogen Oxide
  • R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
  • X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -).
  • the silicon source is selected from the group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite, and orthosilica At least one of the group consisting of tetraethyl acid;
  • the germanium source is selected from the group consisting of germanium oxide, germanium nitrate and tetraalkoxy germanium (where alkoxy refers to C 1 -C 6 alkoxy) At least one of.
  • the organic template Q the silicon source (calculated by SiO 2 ), the germanium source (calculated by GeO 2 ), the fluorine source (calculated by F) and the moles of water
  • the fluorine source includes at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride, preferably hydrogen At least one of the group consisting of hydrofluoric acid and ammonium fluoride.
  • crystallization conditions include crystallization at 100-200°C for 30-400 hours; preferably 110-190°C for 48-360 hours; more preferably 120- Crystallize at 180°C for 72-320 hours.
  • the mixture also includes a source of elements other than silicon and germanium, preferably selected from a source of boron, aluminum, gallium, titanium, zirconium, and hafnium Source, tin source, zinc source, iron source, chromium source and indium source; more preferably selected from the group consisting of boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, zirconium oxide source, oxide At least one oxide source in the group consisting of a hafnium source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source; the oxide source (based on the corresponding oxide)
  • the molar ratio of the germanium source (calculated as GeO 2 ) is (0.01-0.1):1, preferably (0.015-0.08):1.
  • a molecular sieve composition comprising the molecular sieve of any one of the above technical solutions or a molecular sieve synthesized according to the preparation method of any one of the above technical solutions, and a binder.
  • the silicon and germanium-based molecular sieves involved have a framework structure that has never been obtained before in the field.
  • the silicon and germanium-based molecular sieve has a regular molecular size pore structure, strong acidity, ion exchange performance and high thermal stability.
  • the related preparation method of molecular sieve based on silicon and germanium has simple synthesis steps, strong operability, wide synthesis range, and is convenient for promotion.
  • the present invention also provides the following embodiments:
  • a molecular sieve SCM-25 said SCM-25 molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5;
  • 0.05 ⁇ k ⁇ 1.0 preferably 0.05 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.4;
  • Q is an organic template, 0.01 ⁇ m ⁇ 1.0, preferably 0.02 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.3; the organic template is selected from containing 1,1,3,5 -Tetraalkylpiperidinium ion or quaternary ammonium form as shown in the following structural formula, preferably 1,1,3,5-tetramethylpiperidine hydroxide;
  • R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
  • X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -);
  • a preparation method of SCM-25 molecular sieve comprising combining silicon source, germanium source, fluorine source, organic template Q and water or a mixture formed by silicon source, germanium source, fluorine source, organic template Q and water The step of crystallization to obtain the molecular sieve; and optionally, the step of calcining the obtained molecular sieve;
  • the organic template Q is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-tetramethylpiperidine hydrogen Oxide
  • R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
  • X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -).
  • the silicon source is selected from the group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, At least one selected from the group consisting of zeolite molecular sieve and tetraethylorthosilicate;
  • the germanium source is selected from at least one selected from the group consisting of germanium oxide, germanium nitrate and tetraalkoxy germanium;
  • the fluorine source includes at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride It is preferably at least one of the group consisting of hydrofluoric acid and ammonium fluoride.
  • crystallization conditions include crystallization at 100-200°C for 30-400 hours; preferably 110-190°C for 48-360 hours ; It is more preferable to crystallize at 120-180°C for 72-320 hours.
  • the mixture also includes a source of elements other than silicon and germanium, preferably selected from boron source, aluminum source, gallium source, titanium source, At least one of zirconium source, hafnium source, tin source, zinc source, iron source, chromium source and indium source; more preferably selected from boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, oxide source At least one oxide source in the group consisting of a zirconium source, a hafnium oxide source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source;
  • a source of elements other than silicon and germanium preferably selected from boron source, aluminum source, gallium source, titanium source, At least one of zirconium source, hafnium oxide source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source;
  • the molar ratio of the oxide source (based on the corresponding oxide) to the germanium source (based on GeO 2 ) is (0.01-0.1):1, preferably (0.015-0.08):1.
  • a molecular sieve composition comprising the molecular sieve SCM-25 of any one of embodiments 1 to 6 or a molecular sieve SCM-25 synthesized according to the method of synthesizing the molecular sieve SCM-25 of any one of embodiments 7 to 11, and Knot agent.
  • Figure 1 is an X-ray diffraction (XRD) pattern of the sample obtained in Example 1 before firing;
  • Figure 2 is an X-ray diffraction (XRD) pattern of the sample obtained in Example 1 after firing;
  • Figure 3 is a scanning electron microscope (SEM) photograph of the sample obtained in Example 1;
  • Figure 4 is the N 2 adsorption-desorption isotherm of the sample obtained in Example 1 at 77K;
  • the silicon and germanium-based molecular sieve of the present invention is sometimes also referred to as the molecular sieve of the present invention, or SCM-25 molecular sieve, or SCM-25 molecular sieve based on silicon and germanium.
  • the expression "the molecular sieve is based on silicon and germanium” or a similar expression means that the framework of the molecular sieve contains silicon and germanium. In a special case, this type of expression may mean that the framework of the molecular sieve consists only of silicon and germanium.
  • the expression "not more than 10% of the 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 the Ge atoms in the molecular sieve framework are replaced by at least one element other than silicon and germanium.
  • the elements of silicon and germanium are substituted by atoms, and this substituted element occupies the position before the Ge atom.
  • the so-called specific surface area refers to the total area of a sample per unit mass, including internal surface area and external surface area.
  • Non-porous samples have only external surface area, such as Portland cement, some clay mineral particles, etc.; porous and porous samples have external surface area and internal surface area, such as asbestos fiber, diatomaceous earth, and molecular sieves.
  • the surface area of pores with a pore diameter of less than 2nm in porous and porous samples is the internal surface area.
  • the surface area after deducting the internal surface area is called the external surface area.
  • the external surface area per unit mass sample is the external specific surface area.
  • the so-called pore volume refers to the volume of pores per unit mass of a porous material.
  • the so-called 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 counted).
  • the so-called micropore volume refers to the volume of all micropores per unit mass of molecular sieve (generally refers to pores with a channel diameter of less than 2nm).
  • w, m, s, and vs represent the intensity of diffraction peaks, w is weak, m is medium, s is strong, and vs is very strong, which is understood by those skilled in the art.
  • w is less than 20%; m is 20%-40% (not including 40%); s is 40%-70%; vs is greater than 70%, where the percentage is relative to the maximum in the XRD spectrum
  • the intensity of the strong peak, that is, the strongest peak in the XRD spectrum is defined as 100%.
  • XRD X-ray diffraction spectrum
  • a molecular sieve based on silicon and germanium which has an X-ray diffraction pattern substantially as shown in the following table:
  • the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
  • the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
  • the molecular sieve of the present invention has a schematic chemical composition I as shown in the formula "SiO 2 ⁇ 1/nGeO 2 ". It is known that molecular sieves sometimes (especially immediately after synthesis) contain a certain amount of water, but the present invention does not believe that it is necessary to limit the amount of water, because the presence or absence of water does not substantially Affect the XRD spectrum of the molecular sieve. In view of this, the schematic chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Moreover, it is obvious that the schematic chemical composition I represents the framework chemical composition of the molecular sieve of the present invention.
  • the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5.
  • the molecular sieve may generally further contain organic matter (especially organic template) and water, such as those filled in its pores. Therefore, the molecular sieve of the present invention may also have a schematic chemical composition II as shown in the formula "kF ⁇ mQ ⁇ SiO 2 ⁇ 1/nGeO 2 ⁇ pH 2 O".
  • the molecular sieve with the schematic chemical composition I can be obtained.
  • the firing can be carried out in any manner conventionally known in the art.
  • the firing temperature is generally from 300°C to 750°C, preferably from 400°C to 600°C, and the firing time is generally from 1 hour to 10 hours, preferably From 3 hours to 6 hours.
  • the firing can be carried out in an oxygen-containing atmosphere, such as air or oxygen atmosphere, and the firing can also be carried out in situ.
  • the schematic chemical composition I is sometimes also called the schematic chemical composition after calcination
  • the schematic chemical composition II is sometimes also called the synthetic schematic chemical composition.
  • the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5.
  • F is fluorine, and 0.05 ⁇ k ⁇ 1.0, preferably 0.05 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.4.
  • Q is an organic template, 0.01 ⁇ m ⁇ 1.0, preferably 0.02 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.3.
  • the organic template is selected from the group containing 1,1,3,5-tetraalkylpiperidinium ion or the quaternary ammonium form represented by the following structural formula, 1,1,3,5-tetramethylpiperidine hydroxide is preferred.
  • These organic templating agents can be used singly or in combination of multiple in a desired ratio.
  • R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
  • X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -);
  • 0.005 ⁇ p ⁇ 0.5 preferably 0.01 ⁇ p ⁇ 0.4, more preferably 0.01 ⁇ p ⁇ 0.3, more preferably 0.02 ⁇ p ⁇ 0.2.
  • the framework germanium can be partially replaced by trivalent or tetravalent elements other than silicon and germanium, and the replacement rate does not exceed 10%.
  • the parameter "replacement rate" is dimensionless.
  • the element other than silicon and germanium is selected from at least one of the group consisting of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium and indium, and is preferably selected from the group consisting of aluminum and titanium At least one of.
  • the substitution rate 2X 2 O 3 /(2X 2 O 3 +GeO 2 ) ⁇ 100%, where X is a trivalent element; germanium is tetravalent
  • the substitution rate YO 2 /(YO 2 +GeO 2 ) ⁇ 100%, where Y is a tetravalent element.
  • the specific surface area (BET method) of the molecular sieve of the present invention is 200-800 m 2 /g, preferably 250-700 m 2 /g.
  • the pore volume (t-plot method) of the molecular sieve of the present invention is 0.1-0.35 cm 3 /g, preferably 0.12-0.3 cm 3 /g.
  • the molecular sieve of the present invention can be synthesized by the following method.
  • the present invention also relates to a method for preparing a molecular sieve based on silicon and germanium, which includes combining a silicon source, a germanium source, a fluorine source, an organic template agent Q and water or a silicon source, a germanium source, a fluorine source, and an organic template.
  • the step of crystallizing the mixture of agent Q and water hereinafter collectively referred to as mixture to obtain the molecular sieve.
  • the organic template in the preparation method of the molecular sieve, is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-Tetramethylpiperidine hydroxide.
  • These organic templating agents can be used singly or in combination of multiple in a desired ratio.
  • R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
  • X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -).
  • the crystallization step can be performed in any manner conventionally known in the art.
  • any silicon source conventionally used in the art for this purpose can be used.
  • water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite, or tetraethylorthosilicate, etc. can be mentioned.
  • These silicon sources can be used singly or in combination of multiple in a desired ratio.
  • germanium source any germanium source conventionally used in the art for this purpose can be used, including but not limited to germanium oxide, germanium nitrate and tetraalkoxy.
  • germanium oxide germanium oxide
  • germanium nitrate germanium nitrate
  • tetraalkoxy germanium oxide
  • alkoxy refers to C 1 -C 6 alkoxy.
  • any fluorine source conventionally used in the art for this purpose can be used, for example, fluoride or its aqueous solution, such as hydrofluorine Acid, ammonium fluoride, sodium fluoride, potassium fluoride, especially hydrofluoric acid.
  • fluoride or its aqueous solution such as hydrofluorine Acid, ammonium fluoride, sodium fluoride, potassium fluoride, especially hydrofluoric acid.
  • the crystallization conditions include: crystallization at 100-200°C for 30-400 hours; preferably 110-190°C for 48-360 hours; more preferably 120 Crystallize at -185°C for 72-320 hours, for example at 120-180°C for 72-320 hours.
  • the source of valence elements is preferably a source of oxides of trivalent or tetravalent elements other than silicon and germanium.
  • the oxide source it is preferably selected from boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, zirconium oxide source, hafnium oxide source, tin oxide source, zinc oxide source, iron oxide source, chromium oxide source and At least one oxide source in the group consisting of indium oxide sources; as the alumina source, specific examples include those selected from the group consisting of aluminum hydroxide, sodium aluminate, aluminum salt, kaolin and montmorillonite At least one.
  • the boron oxide source include at least one selected from the group consisting of boron oxide, borax, sodium metaborate, and boric acid.
  • the tin oxide source include at least one selected from the group consisting of tin tetrachloride, stannous chloride, alkyl tin, tin alkoxide, and organotinate.
  • the zirconium oxide source include at least one selected from the group consisting of zirconium salts (such as zirconium nitrate and zirconium sulfate), alkyl zirconium, zirconium alkoxide, and organic zirconate.
  • titanium oxide source specific examples include tetraalkyl titanates (such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra n-butyl titanate), TiCl 4 One or more of hexafluorotitanic acid, Ti(SO 4 ) 2 and their hydrolyzed products.
  • tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra n-butyl titanate
  • TiCl 4 One or more of hexafluorotitanic acid
  • Ti(SO 4 ) 2 titanium oxide source
  • gallium oxide source specific examples include those selected from gallium nitrate, gallium oxide, gallium halides (such as gallium chloride, gallium bromide), gallium sulfate, gallium isopropoxide, gallium acetate, and gallium ethoxylate
  • hafnium oxide source specific examples include hafnium oxide, hafnium halides (such as hafnium chloride, hafnium bromide), hafnium sulfate, hafnium tert-butoxide, hafnium oxychloride, At least one of the group consisting of hafnium ethoxylate;
  • zinc oxide source specific examples include those selected from zinc oxide, zinc halide (such as zinc chloride), zinc acetate, basic zinc carbonate, zinc sulfate, At least one of the group consisting of zinc nitrate, zinc lactate, and zinc gluconate;
  • iron oxide source specific examples include those selected from iron sulfate, iron nitrate, iron halides (such as iron trichloride), and At least one of the group consisting of iron and iron citrate;
  • chromium oxide source specific examples include those selected from the group consisting of chromium trioxide, chromine
  • the molar ratio of the oxide source (calculated by the corresponding oxide) to the germanium source (calculated by GeO 2 ) is generally It is (0.01-0.1):1, preferably (0.015-0.08):1.
  • the molecular sieve in the preparation method of the molecular sieve, after the crystallization is completed, the molecular sieve can be separated from the obtained reaction mixture as a product by any conventionally known separation method, thereby obtaining the product.
  • the molecular sieve of the invention is also referred to as the molecular sieve of the invention in a synthetic state.
  • the separation method for example, a method of filtering, washing and drying the obtained reaction mixture can be cited.
  • the filtering, washing and drying can be performed in any manner conventionally known in the art.
  • the obtained reaction mixture may be simply filtered with suction.
  • washing for example, washing with deionized water is used.
  • drying temperature for example, 40 to 250°C, preferably 60 to 150°C, and as the drying time, for example, 8 to 30 hours, preferably 10 to 20 hours. This drying may be carried out under normal pressure or under reduced pressure.
  • the molecular sieve obtained by crystallization can be calcined as required to remove the organic template and possible moisture, etc., thereby obtaining the calcined Molecular sieve, also known as the molecular sieve of the present invention in its calcined form.
  • the firing can be carried out in any manner conventionally known in the art, for example, the firing temperature is generally 300 to 800°C, preferably 400 to 650°C, and the firing time is generally 1 to 10 hours, preferably 3 to 6 hours.
  • the calcination can be performed in an oxygen-containing atmosphere, such as air or oxygen; the calcination can also be performed in situ. Preferably, roasting is performed in situ.
  • the molecular sieve of the present invention can be in any physical form, such as powder, granules or molded products (such as strips, clover, etc.). These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.
  • the molecular sieve of the present invention can be used in combination with other materials, thereby obtaining a molecular sieve composition.
  • these other materials include active materials and inactive materials.
  • the active material include synthetic zeolite and natural zeolite
  • examples of the inactive material (generally referred to as a binder) include clay, clay, silica gel, and alumina. These other materials can be used alone or in combination of multiple types in any ratio.
  • the amount of the other materials you can directly refer to the conventional amount in this field, and there is no particular limitation.
  • the molecular sieve or the molecular sieve composition of the present 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. Therefore, at least one component can be partially or substantially separated from the mixture of various components by contacting the mixture with the molecular sieve or the molecular sieve composition of the present invention to selectively adsorb this component.
  • the molecular sieve or the molecular sieve composition of the present invention can also be used as a catalyst (or as its catalytically active component) directly or after necessary processing or transformation (such as ion exchange, etc.) for molecular sieves conventionally performed in the art. Minute).
  • reactants such as hydrocarbons
  • the target product can be obtained.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 170°C for crystallization for 288 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain a molecular sieve.
  • the product molecular sieve has a specific surface area of 498 m 2 /g and a micropore volume of 0.18 cm 3 /g.
  • the XRD pattern of the sample before calcination is shown in Fig. 1, the XRD pattern after calcination is shown in Fig. 2, the scanning electron microscope picture is shown in Fig. 3, the N 2 adsorption-desorption isotherm at 77K temperature is shown in Fig. 4, molecular sieve
  • the skeleton structure diagram is shown in Figure 5.
  • the XRD pattern of the product obtained after in-situ calcination of the sample before calcination is consistent with Figure 1, and the characteristic data of the XRD pattern and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in an oven at 160° C. for crystallization for 240 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain molecular sieves.
  • the XRD pattern is similar to Figure 2.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 175°C for crystallization for 216 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain molecular sieves.
  • the XRD pattern is similar to Figure 2.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in an oven at 165°C for crystallization for 180 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain molecular sieves.
  • the XRD pattern is similar to Figure 2.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in a 150°C oven for crystallization for 192 hours. After the reaction, the solids are filtered, washed, dried, and calcined to obtain molecular sieves.
  • the XRD pattern is similar to Figure 2.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with a polytetrafluoroethylene lining, and placed in an oven at 165° C. for crystallization for 250 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is an aluminum-containing molecular sieve.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with a polytetrafluoroethylene lining, and placed in an oven at 155°C for crystallization for 300 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is aluminum-containing molecular sieve.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 185°C for crystallization for 168 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is an aluminum-containing molecular sieve.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 130°C for crystallization for 192 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is an iron-containing molecular sieve.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 175°C for crystallization for 144 hours. After the reaction, the solid is filtered, washed, dried, and calcined to obtain a titanium-containing molecular sieve.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
  • the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in an oven at 180°C for crystallization for 168 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is a molecular sieve containing boron and titanium.
  • the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.

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Abstract

一种基于硅和锗的分子筛、其制备方法及其用途，该分子筛具有如式"SiO 2·1/n GeO 2"所示的示意性化学组成，其中硅锗摩尔比0.1≤n≤30。该分子筛具有独特的X射线衍射图谱，在吸附分离、离子交换、有机物化合物催化转化方面具有良好的应用前景。

Description

基于硅和锗的SCM-25分子筛、其制备方法及其用途 技术领域
本发明涉及一种SCM-25分子筛、其合成方法及其用途。
技术背景
分子筛是一类多孔的结晶材料，目前发现的已知结构的分子筛种类已达245种，并且新结构的分子筛还在不断地涌现出来。因具有规整的分子尺寸孔道结构、较强的酸性和高的水热稳定性，分子筛被广泛应用于催化、吸附和离子交换等领域中，并起着不可替代的作用。分子筛的骨架通常由配位四面体(TO 4)通过共顶点(一般为氧原子)连接而成。对于分子筛来说，骨架中的四面体主要为SiO 4四面体和AlO 4四面体，这两种四面体可以分别被其它的四面体所取代，从而形成不同骨架结构的分子筛或类分子筛。例如，AlO 4四面体可以被GaO 4或ZnO 4四面体取代，从而与SiO 4四面体一道构成杂原子分子筛的骨架；而Ge与Si具有相似的配位性质，也可以形成四面体配位结构，通过GeO 4和SiO 4的联接可以形成数量众多的新型含锗分子筛或类分子筛结构。
1959年Barrer等人首次尝试将Ge元素引入分子筛合成中，制备得到了与A型和X型分子筛具有类似结构的锗酸铝盐(J.Chem.Soc.,1959,195-208)。大约40年后，Yaghi首次制备了含锗的新结构分子筛ASU-7(J.Am.Chem.Soc.1998,120,10569-10570)，这种分子筛的骨架结构完全由GeO 4四面体构成。此后，众多研究者开始尝试合成含锗的新结构分子筛，其中以西班牙巴伦西亚理工大学Corma教授课题组的工作最为瞩目。研究较多的几种硅锗酸盐分子筛包括UTL(US 7074385)、BEC(US 6896869)、STW(Nature Mater.,2008,7,381-385)等。
发明内容
本发明提供一种基于硅和锗的分子筛以及该分子筛的合成方法。
本发明采取的技术方案如下：
1.一种分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
2θ(°)
6.53±0.3
7.05±0.3
9.56±0.3
10.77±0.3
12.84±0.3
18.80±0.3
22.60±0.3
优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
2θ(°)
7.81±0.3
14.37±0.3
14.76±0.3
15.45±0.3
16.35±0.3
17.52±0.3
19.79±0.3
更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
2θ(°)
21.46±0.3
22.04±0.3
23.64±0.3
24.54±0.3
25.14±0.3
26.11±0.3。
2.一种分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
Figure PCTCN2020100969-appb-000001
优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
Figure PCTCN2020100969-appb-000002
Figure PCTCN2020100969-appb-000003
更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
Figure PCTCN2020100969-appb-000004
3.一种分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
2θ(°)
6.53±0.15
7.05±0.15
9.56±0.15
10.77±0.15
12.84±0.15
18.80±0.15
22.60±0.15
优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
2θ(°)
7.81±0.15
14.37±0.15
14.76±0.15
15.45±0.15
16.35±0.15
17.52±0.15
19.79±0.15
更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X- 射线衍射峰，
2θ(°)
21.46±0.15
22.04±0.15
23.64±0.15
24.54±0.15
25.14±0.15
26.11±0.15。
4.一种分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
2θ(°) 相对强度(I/I 0)×100
6.53±0.15 m或s
7.05±0.15 vs
9.56±0.15 w或m
10.77±0.15 s
12.84±0.15 w或m
18.80±0.15 m或s
22.60±0.15 m或s
优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
2θ(°) 相对强度(I/I 0)×100
7.81±0.15 w
14.37±0.15 w
14.76±0.15 w
15.45±0.15 w
16.35±0.15 w
17.52±0.15 w
19.79±0.15 w
更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
2θ(°) 相对强度(I/I 0)×100
21.46±0.15 w或m
22.04±0.15 w或m
23.64±0.15 m
24.54±0.15 m
25.14±0.15 m
26.11±0.15 w或m。
5.一种分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
2θ(°)
6.995±0.200
10.730±0.200
22.515±0.200
6.505±0.200
18.755±0.200
优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
2θ(°)
23.585±0.200
24.470±0.200
25.065±0.200
21.980±0.200
7.870±0.200
9.560±0.200
更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
2θ(°)
12.845±0.200
14.320±0.200
14.725±0.200
15.380±0.200
16.295±0.200
17.490±0.200
19.745±0.200
21.400±0.200
26.055±0.200。
6.一种分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
2θ(°) 相对强度
6.995±0.200 vs
10.730±0.200 s
22.515±0.200 s
6.505±0.200 m或s
18.755±0.200 m或s
优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
2θ(°) 相对强度
23.585±0.200 m
24.470±0.200 m
25.065±0.200 m
21.980±0.200 w或m
7.870±0.200 w
9.560±0.200 w
更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
2θ(°) 相对强度
12.845±0.200 w
14.320±0.200 w
14.725±0.200 w
15.380±0.200 w
16.295±0.200 w
17.490±0.200 w
19.745±0.200 w
21.400±0.200 w
26.055±0.200 w。
7.根据上述技术方案中任一项的分子筛，其中所述分子筛是基于硅和锗的。
8.根据上述技术方案中任一项的分子筛，其中所述分子筛的在77K温度下的N 2吸附-脱附等温线中不存在滞后环。
9.根据上述技术方案中任一项的分子筛，所述分子筛焙烧后的形式中具有如式“SiO 2·1/n GeO 2”所示的示意性化学组成，其中硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5。
10.根据上述技术方案中任一项的分子筛，所述分子筛合成态的形式中 具有如式“kF·mQ·SiO 2·1/nGeO 2·pH 2O”所示的示意性化学组成，其中，硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5；0.05≤k≤1.0，优选0.05≤k≤0.5，更优选0.1≤k≤0.5，更优选0.1≤k≤0.4；Q为有机模板剂，0.01≤m≤1.0，优选0.02≤m≤0.5，更优选0.05≤m≤0.5，更优选0.05≤m≤0.3；所述有机模板剂选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物；
Figure PCTCN2020100969-appb-000005
在上式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3，X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧根离子(OH -)；0.005≤p≤0.5，优选0.01≤p≤0.4，更优选0.01≤p≤0.3，更优选0.02≤p≤0.2。
11.根据上述技术方案中任一项的分子筛，所述分子筛中不超过10％的Ge原子被至少一种非硅和锗的元素的原子取代。
12.根据上述技术方案中任一项的分子筛，所述非硅和锗的元素选自由硼、铝、镓、钛、锆、铪、锡、锌、铁、铬和铟组成的组中的至少一种，优选选自由铝和钛组成的组中的至少一种。
13.一种基于硅和锗的分子筛的制备方法，包括将包含硅源、锗源、氟源、有机模板剂Q和水或者由硅源、锗源、氟源、有机模板剂Q和水形成的混合物晶化以获得所述分子筛的步骤；和任选地，焙烧所述获得的分子筛的步骤；
其中所述有机模板剂Q选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物；
Figure PCTCN2020100969-appb-000006
在式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3，X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧 根离子(OH -)。
14.根据上述技术方案中任一项的分子筛的制备方法，所述硅源选自由水玻璃、硅溶胶、固体硅胶、气相白炭黑、无定形二氧化硅、硅藻土、沸石、正硅酸四乙酯组成的组中的至少一种；所述锗源选自由氧化锗、硝酸锗和四烷氧基锗(其中烷氧基是指C 1-C 6烷氧基)组成的组中的至少一种。
上述技术方案中，所述有机模板剂Q、所述硅源(以SiO 2为计)、所述锗源(以GeO 2为计)、所述氟源(以F为计)和水的摩尔比为Q:SiO 2:GeO 2:F:H 2O＝0.15-4:1:0.033-10:0.2-4:0.5-50，优选Q:SiO 2:GeO 2:F:H 2O＝0.25-3.5:1:0.05-4:0.35-3.5:1-35，更优选Q:SiO 2:GeO 2:F:H 2O＝0.3-2.5:1:0.067-2:0.4-2.5:1.5-25，更优选Q:SiO 2:GeO 2:F:H 2O＝0.35-1.5:1:0.2-1:0.45-2:2-15。
15.根据上述技术方案中任一项的分子筛的制备方法，所述氟源包括选自由氢氟酸、氟化铵、氟化钠、氟化钾组成的组中的至少一种，优选为氢氟酸、氟化铵组成的组中的至少一种。
16.根据上述技术方案中任一项的分子筛的制备方法，所述晶化条件包括在100-200℃晶化30-400小时；优选110-190℃晶化48-360小时；更优选120-180℃晶化72-320小时。
17.根据上述技术方案中任一项的分子筛的制备方法，所述混合物中还包括含非硅和锗的元素源，优选选自由硼源、铝源、镓源、钛源、锆源、铪源、锡源、锌源、铁源、铬源和铟源组成的组中的至少一种；更优选选自由氧化硼源、氧化铝源、氧化镓源、氧化钛源、氧化锆源、氧化铪源、氧化锡源、氧化锌源、氧化铁源、氧化铬源和氧化铟源组成的组中的至少一种氧化物源；所述氧化物源(以相应的氧化物为计)与所述锗源(以GeO 2为计)的摩尔比为(0.01-0.1):1，优选(0.015-0.08):1。
18.一种分子筛组合物，包含上述技术方案中任一项的分子筛或者按照上述技术方案中任一项的分子筛的制备方法合成的分子筛，以及粘结剂。
19.一种上述技术方案中任一项的分子筛、按照上述技术方案中任一项的分子筛的制备方法合成的分子筛、或者上述技术方案中任一项的分子筛组合物作为吸附剂或催化剂的应用。
根据本发明，所涉及的基于硅和锗的分子筛，其骨架结构是本领域之前从未获得过的。
根据本发明，所涉及的基于硅和锗的分子筛，具备规整的分子尺寸孔道结构、较强的酸性、离子交换性能和高的热稳定性。
根据本发明，所涉及的基于硅和锗的分子筛的制备方法，合成步骤简单、可操作性强，合成范围广，便于进行推广。
在本发明的一个方面中，本发明还提供了下列实施方案：
1、一种分子筛SCM-25，所述SCM-25分子筛具有基本上如下表所示的X射线衍射图谱：
Figure PCTCN2020100969-appb-000007
2、根据实施方案1所述的分子筛SCM-25，其特征在于，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
Figure PCTCN2020100969-appb-000008
所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
Figure PCTCN2020100969-appb-000009
3、根据实施方案1所述的分子筛SCM-25，其特征在于，所述分子筛焙烧后的形式中具有如式“SiO 2·1/nGeO 2”所示的示意性化学组成，其中硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5。
4、根据实施方案1所述的分子筛SCM-25，其特征在于，所述分子筛合成态的形式中具有如式“kF·mQ·SiO 2·1/nGeO 2·pH 2O”所示的示意性化学组成，其中，
硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5；
0.05≤k≤1.0，优选0.05≤k≤0.5，更优选0.1≤k≤0.5，更优选0.1≤k≤0.4；
Q为有机模板剂，0.01≤m≤1.0，优选0.02≤m≤0.5，更优选0.05≤m≤0.5，更优选0.05≤m≤0.3；所述有机模板剂选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物；
Figure PCTCN2020100969-appb-000010
在上式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3，X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧根离子(OH -)；
0.005≤p≤0.5，优选0.01≤p≤0.4，更优选0.01≤p≤0.3，更优选0.02≤p≤0.2。
5、根据实施方案1所述的分子筛SCM-25，其特征在于，所述分子筛中不超过10％的Ge原子被至少一种非硅和锗的元素的原子取代。
6、根据实施方案5所述的分子筛SCM-25，其特征在于，所述非硅和锗的元素选自由硼、铝、镓、钛、锆、铪、锡、锌、铁、铬和铟组成的组中的至少一种，优选选自由铝和钛组成的组中的至少一种。
7、一种SCM-25分子筛的制备方法，包括将包含硅源、锗源、氟源、有机模板剂Q和水或者由硅源、锗源、氟源、有机模板剂Q和水形成的混合物晶化以获得所述分子筛的步骤；和任选地，焙烧所述获得的分子筛的步骤；
其中所述有机模板剂Q选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物；
Figure PCTCN2020100969-appb-000011
在式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3， X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧根离子(OH -)。
8、根据实施方案7所述分子筛SCM-25的合成方法，其特征在于，所述硅源选自由水玻璃、硅溶胶、固体硅胶、气相白炭黑、无定形二氧化硅、硅藻土、沸石分子筛、正硅酸四乙酯组成的组中的至少一种；所述锗源选自由氧化锗、硝酸锗和四烷氧基锗组成的组中的至少一种；
所述有机模板剂Q、所述硅源(以SiO 2为计)、所述锗源(以GeO 2为计)、所述氟源(以F为计)和水的摩尔比为Q:SiO 2:GeO 2:F:H 2O＝0.15～4:1:0.033～10:0.2～4:0.5～50，优选Q:SiO 2:GeO 2:F:H 2O＝0.25～3.5:1:0.05～4:0.35～3.5:1～35，更优选Q:SiO 2:GeO 2:F:H 2O＝0.3～2.5:1:0.067～2:0.4～2.5:1.5～25，更优选Q:SiO 2:GeO 2:F:H 2O＝0.35～1.5:1:0.2～1:0.45～2:2～15。
9、根据实施方案7所述分子筛SCM-25的合成方法，其特征在于，所述氟源包括选自由氢氟酸、氟化铵、氟化钠、氟化钾组成的组中的至少一种，优选为氢氟酸、氟化铵组成的组中的至少一种。
10、根据实施方案7所述的SCM-25分子筛的合成方法，其特征在于，所述晶化条件包括在100～200℃晶化30～400小时；优选110～190℃晶化48～360小时；更优选120～180℃晶化72～320小时。
11、根据实施方案7所述分子筛SCM-25的合成方法，其特征在于，所述混合物中还包括含非硅和锗的元素源，优选选自由硼源、铝源、镓源、钛源、锆源、铪源、锡源、锌源、铁源、铬源和铟源组成的组中的至少一种；更优选选自由氧化硼源、氧化铝源、氧化镓源、氧化钛源、氧化锆源、氧化铪源、氧化锡源、氧化锌源、氧化铁源、氧化铬源和氧化铟源组成的组中的至少一种氧化物源；
所述氧化物源(以相应的氧化物为计)与所述锗源(以GeO 2为计)的摩尔比为(0.01～0.1):1，优选(0.015～0.08):1。
12、一种分子筛组合物，包含实施方案1至6任一所述的分子筛SCM-25或者按照实施方案7至11任一所述分子筛SCM-25的合成方法合成的分子筛SCM-25，以及粘结剂。
13、实施方案1至6任一所述的分子筛SCM-25、按照实施方案7至11任一所述分子筛SCM-25的合成方法合成的分子筛SCM-25、或者实施方案12所述分子筛组合物作为吸附剂或催化剂的应用。
附图说明
图1为实施例1所获得样品焙烧前的X射线衍射(XRD)图；
图2为实施例1所获得样品焙烧后的X射线衍射(XRD)图；
图3为实施例1所获得样品的扫描电子显微镜(SEM)照片；
图4为实施例1所获得样品在77K条件下的N 2吸-脱附等温线；
具体实施方式
为了便于理解本发明，本发明列举实施例如下。但是本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应该视为对本发明的具体限制。在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
在本说明书的上下文中，本发明的基于硅和锗的分子筛有时也称为本发明的分子筛，或者SCM-25分子筛，或者基于硅和锗的SCM-25分子筛。
在本说明书的上下文中，表述“所述分子筛是基于硅和锗的”或类似表述是指所述分子筛的骨架包含硅和锗。在一种特殊的情况中，这类表述可以是指所述分子筛的骨架仅仅由硅和锗组成。
在本说明书的上下文中，表述“所述分子筛中不超过10％的Ge原子被至少一种非硅和锗的元素的原子取代”或类似表述是指分子筛骨架中的Ge原子被至少一种非硅和锗的元素的原子取代，而这种取代元素占据了Ge原子之前的位置。在本说明书的上下文中，所谓比表面积，是指单位质量样品所具有的总面积，包括内表面积和外表面积。非孔性样品只具有外表面积，如硅酸盐水泥、一些粘土矿物粉粒等；有孔和多孔样品具有外表面积和内表面积，如石棉纤维、硅藻土和分子筛等。有孔和多孔样品中孔径小于2nm的孔的表面积是内表面积，扣除内表面积后的表面积称为外表面积，单位质量样品具有的外表面积即外比表面积。
在本说明书的上下文中，所谓孔容，指单位质量多孔材料所具有的孔的容积。所谓总孔容，是指单位质量分子筛所具有的全部孔(一般仅计入孔道直径小于50nm的孔)的容积。所谓微孔孔容，是指单位质量分子筛所具有的全部微孔(一般指的是孔道直径小于2nm的孔)的容积。
在本说明书的上下文中，在分子筛的XRD数据中，w、m、s、vs代表 衍射峰强度，w为弱，m为中等，s为强，vs为非常强，这为本领域技术人员所熟知的。一般而言，w为小于20％；m为20％-40％(不包括40％)；s为40％-70％；vs为大于70％，其中所述百分数是相对于XRD谱图中最强峰，即XRD谱图中最强峰的强度定义为100％。
在本说明书的上下文中，分子筛的结构是由X-射线衍射谱图(XRD)确定的，所述分子筛的X-射线衍射谱图(XRD)由X-射线粉末衍射仪测定，使用Cu-Kα射线源，Kα1波长λ＝1.5405980埃
Figure PCTCN2020100969-appb-000012
镍滤光片。
需要特别说明的是，在本说明书的上下文中公开的两个或多个方面(或实施方式)可以彼此任意组合，由此而形成的技术方案(比如方法或系统)属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围之内。
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，除非以重量为基准时不符合本领域技术人员的常规认识。
根据本发明的一个方面，涉及一种基于硅和锗的分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
Figure PCTCN2020100969-appb-000013
根据本发明的一个方面，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
Figure PCTCN2020100969-appb-000014
根据本发明的一个方面，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
Figure PCTCN2020100969-appb-000015
根据本发明的一个方面，本发明的分子筛具有如式“SiO 2·1/nGeO 2”所示的示意性化学组成I。已知的是，分子筛中有时会(尤其是在刚合成之后)含有一定量的水分，但本发明认为并没有必要对该水分的量进行限定，因为该水分的存在与否并不会实质上影响该分子筛的XRD谱图。鉴于此，所述示意性化学组成实际上代表的是该分子筛的无水化学组成。而且，显然的是，该示意性化学组成I代表的是本发明的分子筛的骨架化学组成。
根据本发明的一个方面，在所述示意性化学组成I中，硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5。
根据本发明的一个方面，在刚合成后，所述分子筛在组成中一般还可能进一步含有有机物(特别是有机模板剂)和水等，比如填充在其孔道中的那些。因此，本发明的分子筛还可能具有如式“kF·mQ·SiO 2·1/nGeO 2·pH 2O”所示的示意性化学组成II。在此，通过焙烧具有所述示意性化学组成II的分子筛，以便脱除其孔道中存在的任何有机模板剂和水等，就可以获得具有所述示意性化学组成I的分子筛。另外，所述焙烧可以按照本领域常规已知的任何方式进行，比如焙烧温度一般为从300℃至750℃，优选从400℃至600℃，而焙烧时间一般为从1小时至10小时，优选从3小时至6小时。另外，所述焙烧可以在含氧气氛下进行，比如空气或者氧气气氛下，焙烧也可以原位进行。鉴于此，所述示意性化学组成I有时也称为焙烧后示意性化学组成，而所述示意性化学组成II有时也称为合成态示意性化学组成。
根据本发明的一个方面，在所述示意性化学组成II中，硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5。
根据本发明的一个方面，在所述示意性化学组成II中，F为氟，0.05≤k≤1.0，优选0.05≤k≤0.5，更优选0.1≤k≤0.5，更优选0.1≤k≤0.4。
根据本发明的一个方面，在所述示意性化学组成II中，Q为有机模板剂， 0.01≤m≤1.0，优选0.02≤m≤0.5，更优选0.05≤m≤0.5，更优选0.05≤m≤0.3。
根据本发明的一个方面，在所述示意性化学组成II中，所述有机模板剂选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物。这些有机模板剂可以单独使用一种，或者以需要的比例组合使用多种。
Figure PCTCN2020100969-appb-000016
在上式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3，X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧根离子(OH -)；
根据本发明的一个方面，在所述示意性化学组成II中，0.005≤p≤0.5，优选0.01≤p≤0.4，更优选0.01≤p≤0.3，更优选0.02≤p≤0.2。
根据本发明的一个方面，在本发明的分子筛中，骨架锗可以部分被非硅和锗的三价或四价元素替代，替代率不超过10％。在此，该参数“替代率”无量纲。所述非硅和锗的元素选自由硼、铝、镓、钛、锆、铪、锡、锌、铁、铬和铟组成的组中的至少一种，优选选自由铝和钛组成的组中的至少一种。锗被三价元素，例如三价硼、三价铝等替代时，替代率＝2X 2O 3/(2X 2O 3+GeO 2)×100％，其中X为三价元素；锗被四价元素，例如四价锡、四价锆、四价钛等替代时，替代率＝YO 2/(YO 2+GeO 2)×100％，其中Y为四价元素。在计算替代率时，使用相应氧化物的摩尔数。
根据本发明的一个方面，本发明的分子筛的比表面积(BET法)为200-800米 2/克，优选250-700米 2/克。
根据本发明的一个方面，本发明的分子筛的微孔孔容(t-plot法)为0.1-0.35厘米 3/克，优选0.12-0.3厘米 3/克。
根据本发明的一个方面，本发明的分子筛可以通过如下的方法进行合成。鉴于此，本发明还涉及一种基于硅和锗的分子筛的制备方法，包括将包含硅源、锗源、氟源、有机模板剂Q和水或者由硅源、锗源、氟源、有机模板剂Q和水形成的混合物(以下统称为混合物)晶化以获得所述分子筛的步骤。
根据本发明的一个方面，在所述分子筛的制备方法中，所述有机模板 剂选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物。这些有机模板剂可以单独使用一种，或者以需要的比例组合使用多种。
Figure PCTCN2020100969-appb-000017
在式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3，X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧根离子(OH -)。
根据本发明的一个方面，在所述分子筛的制备方法中，所述晶化步骤可以按照本领域常规已知的任何方式进行，比如可以举出使所述硅源、所述锗源、所述氟源、所述有机模板剂和水按照预定的比例混合，并使所获得的混合物在所述晶化条件下水热晶化的方法。可以根据需要在搅拌的存在下。
根据本发明的一个方面，在所述分子筛的制备方法中，作为所述硅源，可以使用本领域为此目的而常规使用的任何硅源。比如可以举出水玻璃、硅溶胶、固体硅胶、气相白炭黑、无定形二氧化硅、硅藻土、沸石、或正硅酸四乙酯等。这些硅源可以单独使用一种，或者以需要的比例组合使用多种。
根据本发明的一个方面，在所述分子筛的制备方法中，作为所述锗源，可以使用本领域为此目的而常规使用的任何锗源，包括但不限于氧化锗、硝酸锗和四烷氧基锗，其中烷氧基是指C 1-C 6烷氧基。
根据本发明的一个方面，在所述分子筛的制备方法中，作为所述氟源，可以使用本领域为此目的而常规使用的任何氟源，比如可以举出氟化物或其水溶液，如氢氟酸、氟化铵、氟化钠、氟化钾，特别是氢氟酸等。
根据本发明的一个方面，在所述分子筛的制备方法中，所述有机模板剂Q、所述硅源(以SiO 2为计)、所述锗源(以GeO 2为计)、所述氟源(以F为计)和水的摩尔比为Q:SiO 2:GeO 2:F:H 2O＝0.15-4:1:0.033-10:0.2-4:0.5-50，优选Q:SiO 2:GeO 2:F:H 2O＝0.25-3.5:1:0.05-4:0.35-3.5:1-35，更优选Q:SiO 2:GeO 2:F:H 2O＝0.3-2.5:1:0.067-2:0.4-2.5:1.5-25，更优选Q:SiO 2:GeO 2:F:H 2O＝0.35-1.5:1:0.2-1:0.45-2:2-15。
根据本发明的一个方面，在所述分子筛的制备方法中，所述晶化条件包 括：在100-200℃晶化30-400小时；优选110-190℃晶化48-360小时；更优选120-185℃晶化72-320小时，例如120-180℃晶化72-320小时。
根据本发明的一个方面，在所述分子筛的制备方法中，当采用三价或四价非硅和锗的元素替代锗原子时，需向所述混合物中加入非硅和锗的三价或四价元素源，优选非硅和锗的三价或四价元素的氧化物源。作为所述氧化物源，优选选自由氧化硼源、氧化铝源、氧化镓源、氧化钛源、氧化锆源、氧化铪源、氧化锡源、氧化锌源、氧化铁源、氧化铬源和氧化铟源组成的组中的至少一种氧化物源；作为所述氧化铝源，具体比如可以举出选自由氢氧化铝、铝酸钠、铝盐、高岭土和蒙脱土组成的组中的至少一种。作为所述氧化硼源，具体比如可以举出选自由氧化硼、硼砂、偏硼酸钠和硼酸组成的组中的至少一种。作为所述氧化锡源，具体比如可以举出选自由四氯化锡、氯化亚锡、烷基锡、烷氧基锡和有机锡酸酯组成的组中的至少一种。作为所述氧化锆源，具体比如可以举出选自由锆盐(如硝酸锆、硫酸锆)、烷基锆、烷氧基锆和有机锆酸酯组成的组中的至少一种。作为所述氧化钛源，具体比如可以举出选自四烷基钛酸酯(如钛酸四甲酯、钛酸四乙酯、钛酸四丙酯、钛酸四正丁酯)、TiCl 4、六氟钛酸、Ti(SO 4) 2以及它们的水解产物中的一种或多种。作为所述氧化镓源，具体比如可以举出选自硝酸镓、氧化镓、卤化镓(如氯化镓、溴化镓)、硫酸镓、异丙醇镓、醋酸镓、乙氧基镓组成的组中的至少一种；作为所述氧化铪源，具体比如可以举出选自氧化铪、卤化铪(如氯化铪、溴化铪)、硫酸铪、叔丁醇铪、氧氯化铪、乙氧基铪组成的组中的至少一种；作为所述氧化锌源，具体比如可以举出选自氧化锌、卤化锌(如氯化锌)、乙酸锌、碱式碳酸锌、硫酸锌、硝酸锌、乳酸锌、葡萄糖酸锌组成的组中的至少一种；作为所述氧化铁源，具体比如可以举出选自硫酸铁、硝酸铁、卤化铁(如三氯化铁)、二茂铁、柠檬酸铁组成的组中的至少一种；作为所述氧化铬源，具体比如可以举出选自三氧化二铬、氯化铬、硝酸铬、乙酸铬、硫酸铬钾组成的组中的至少一种；作为所述氧化铟源，具体比如可以举出选自氧化铟、硫酸铟、卤化铟(如三氯化铟)、醋酸铟组成的组中的至少一种。
根据本发明的一个方面，在所述分子筛的制备方法中，在使用时，所述氧化物源(以相应的氧化物为计)与所述锗源(以GeO 2为计)的摩尔比一般为(0.01-0.1):1，优选(0.015-0.08):1。
根据本发明的一个方面，在所述分子筛的制备方法中，在所述晶化完成之后，可以通过常规已知的任何分离方式从所获得的反应混合物中分离 出分子筛作为产品，由此获得本发明的分子筛，也称为合成态形式的本发明的分子筛。作为所述分离方式，比如可以举出对所述获得的反应混合物进行过滤、洗涤和干燥的方法。
根据本发明的一个方面，在所述分子筛的制备方法中，所述过滤、洗涤和干燥可以按照本领域常规已知的任何方式进行。具体举例而言，作为所述过滤，比如可以简单地抽滤所述获得的反应混合物。作为所述洗涤，比如可以举出使用去离子水进行洗涤。作为所述干燥温度，比如可以举出40至250℃，优选60至150℃，作为所述干燥的时间，比如可以举出8至30小时，优选10至20小时。该干燥可以在常压下进行，也可以在减压下进行。
根据本发明的一个方面，在所述分子筛的制备方法中，根据需要，可以将晶化获得的分子筛进行焙烧，以脱除所述有机模板剂和可能存在的水分等，由此获得焙烧后的分子筛，也称为焙烧后形式的本发明分子筛。所述焙烧可以按照本领域常规已知的任何方式进行，比如焙烧温度一般为300至800℃，优选400至650℃，而焙烧时间一般为1至10小时，优选3至6小时。另外，所述焙烧可以在含氧气氛下进行，比如空气或者氧气气氛下；所述焙烧也可以原位进行。优选地，焙烧原位进行。
根据本发明的一个方面，本发明的分子筛可以呈现为任何的物理形式，比如粉末状、颗粒状或者模制品状(比如条状、三叶草状等)。可以按照本领域常规已知的任何方式获得这些物理形式，并没有特别的限定。
根据本发明的一个方面，本发明的分子筛可以与其他材料复合使用，由此获得分子筛组合物。作为这些其他材料，比如可以举出活性材料和非活性材料。作为所述活性材料，比如可以举出合成沸石和天然沸石等，作为所述非活性材料(一般称为粘结剂)，比如可以举出粘土、白土、硅胶和氧化铝等。这些其他材料可以单独使用一种，或者以任意的比例组合使用多种。作为所述其他材料的用量，可以直接参照本领域的常规用量，并没有特别的限制。
根据本发明的一个方面，本发明的分子筛或所述分子筛组合物可用作吸附剂，例如用来在气相或液相中从多种组分的混合物中分离出至少一种组分。所以，至少一种组分可以部分或基本全部从各种组分的混合物中分离出来，方式是让混合物与本发明的分子筛或所述分子筛组合物相接触，有选择的吸附这一组分。
根据本发明的一个方面，本发明的分子筛或所述分子筛组合物还可直接或者经过本领域常规针对分子筛进行的必要处理或转化(比如离子交换等)之后用作催化剂(或作为其催化活性组分)。为此，根据本发明的一个方面，比如可以使反应物(比如烃类)在所述催化剂的存在下进行预定反应，并由此获得目标产物。
结合以下具体实施例，对本发明作进一步的详细说明，本发明的保护内容不局限于以下实施例。
【实施例1】
将7g氧化锗溶于76.8g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入27.8g正硅酸四乙酯(TEOS)，常温下搅拌，水解完全后将容器敞口搅拌过夜以挥发乙醇和部分水，加入5g氢氟酸(40wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
0.5(1,1,3,5-TMPOH):0.667SiO 2:0.333GeO 2:0.5HF:7H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于170℃烘箱中晶化288小时。反应后固体经过滤、洗涤、干燥、在空气中焙烧后得到分子筛，所得产品分子筛的比表面积为498米 2/克，微孔孔容0.18厘米 3/克。样品焙烧前的XRD图谱如图1所示，焙烧后的XRD图谱如图2所示，扫描电镜照片如图3所示，77K温度下N 2吸附-脱附等温线如图4所示，分子筛骨架结构示意图如图5所示。
Figure PCTCN2020100969-appb-000018
Figure PCTCN2020100969-appb-000019
焙烧前样品原位焙烧后得到的产物的XRD图谱与图1一致，并且该XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例2】
将4.2g氧化锗溶于115g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入33.3g正硅酸四乙酯(TEOS)，常温下搅拌，水解完全后将容器敞口搅拌过夜以挥发乙醇和部分水，加入10g氟化铵溶液(37wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
0.75(1,1,3,5-TMPOH):0.8SiO 2:0.2GeO 2:0.5NH 4F:2.5H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于160℃烘箱中晶化240小时。反应后固体经过滤、洗涤、干燥、在空气中焙烧后得到分子筛，XRD图谱与图2类似。
Figure PCTCN2020100969-appb-000020
Figure PCTCN2020100969-appb-000021
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例3】
将10.5g氧化锗溶于61.4g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入20.8g正硅酸四乙酯(TEOS)，常温下搅拌，水解完全后将容器敞口搅拌过夜以挥发乙醇和部分水，加入5g氢氟酸(40wt％)和10g氟化铵溶液(37wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
0.4(1,1,3,5-TMPOH):0.5SiO 2:0.5GeO 2:0.5HF:0.5NH 4F:4.8H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于175℃烘箱中晶化216小时。反应后固体经过滤、洗涤、干燥、在空气中焙烧后得到分子筛，XRD图谱与图2类似。
Figure PCTCN2020100969-appb-000022
Figure PCTCN2020100969-appb-000023
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例4】
将14g氧化锗溶于153.6g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入13.9g正硅酸四乙酯(TEOS)，常温下搅拌，水解完全后将容器敞口搅拌过夜以挥发乙醇和部分水，加入12g氢氟酸(40wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
1(1,1,3,5-TMPOH):0.333SiO 2:0.667GeO 2:1.2HF:13.5H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于165℃烘箱中晶化180小时。反应后固体经过滤、洗涤、干燥、在空气中焙烧后得到分子筛，XRD图谱与图2类似。
Figure PCTCN2020100969-appb-000024
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例5】
将3.5g氧化锗溶于192g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入34.5g正硅酸四乙酯(TEOS)，常温下搅拌，水解完全后将容器敞口搅拌过夜以挥发乙醇和部分水，加入60g氟化铵溶液(37wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
1.25(1,1,2,5-TMPOH):0.833SiO 2:0.167GeO 2:3NH 4F:22H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于150℃烘箱中晶化192小时。反应后固体经过滤、洗涤、干燥、焙烧后得到分子筛，XRD图谱与图2类似。
Figure PCTCN2020100969-appb-000025
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例6】
将0.4g异丙醇铝、7g氧化锗溶于76.8g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入27.8g正硅酸四乙酯(TEOS)，常温下搅拌，水解完全后将容器敞口搅拌过夜以挥发乙醇、丙醇和部分水，加入10g氢氟酸(40wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
0.5(1,1,3,5-TMPOH):0.667SiO 2:0.333GeO 2:0.005Al 2O 3:1HF:5H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于165℃烘箱中晶化250小时。反应后固体经过滤、洗涤、干燥、焙烧后得到的固体为含铝分子筛，XRD图谱与图2类似，产物中(Si+Ge)/Al＝130。
Figure PCTCN2020100969-appb-000026
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例7】
将2g异丙醇铝、10.5g氧化锗溶于76.8g 1,1,3,5-TMPOH水溶液中(20 wt％)，缓慢加入20.8g正硅酸四乙酯(TEOS)，水解完全后将容器敞口搅拌过夜以挥发乙醇、丙醇和部分水，加入10g氢氟酸(40wt％)和10g氟化铵溶液(37wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
0.5(1,1,3,5-TMPOH):0.5SiO 2:0.5GeO 2:0.025Al 2O 3:1HF:0.5NH 4F:8H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于155℃烘箱中晶化300小时。反应后固体经过滤、洗涤、干燥、焙烧后得到的固体为含铝分子筛，XRD图谱与图2类似，产物中(Si+Ge)/Al＝28。
Figure PCTCN2020100969-appb-000027
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例8】
将12.4g氧化锗溶于92g 1,1,3,5-TMPOH水溶液中(20wt％)，加入1g Ludox-AS-40硅溶胶和4.6g USY分子筛(SiO 2/Al 2O 3＝37)，水解完全后将容 器敞口搅拌过夜以挥发部分水，加入28g氟化铵溶液(37wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
0.6(1,1,3,5-TMPOH):0.4SiO 2:0.6GeO 2:0.01Al 2O 3:1.4NH 4F:16.5H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于185℃烘箱中晶化168小时。反应后固体经过滤、洗涤、干燥、焙烧后得到的固体为含铝分子筛，XRD图谱与图2类似，产物中(Si+Ge)/Al＝57。
Figure PCTCN2020100969-appb-000028
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例9】
将7g氧化锗溶于76.8g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入27.8g正硅酸四乙酯(TEOS)，水解完全后加入2g九水合硝酸铁，将容器敞口搅拌过夜以挥发乙醇和部分水，加入5g氢氟酸(40wt％)和30g氟化铵溶液(37wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组 成：
0.5(1,1,3,5-TMPOH):0.667SiO 2:0.333GeO 2:0.0125Fe 2O 3:0.5HF:1.5NH 4F:6.6H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于130℃烘箱中晶化192小时。反应后固体经过滤、洗涤、干燥、焙烧后得到的固体为含铁分子筛，XRD图谱与图2类似，产物中(Si+Ge)/Fe＝30。
Figure PCTCN2020100969-appb-000029
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例10】
将7g氧化锗溶于123g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢加入27.8g正硅酸四乙酯(TEOS)，搅拌均匀后再缓慢滴加1.7g钛酸四丁酯，常温下搅拌，水解完全后将容器敞口搅拌过夜以挥发乙醇、丁醇和部分水，加入20g氢氟酸(40wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩 尔组成：
0.8(1,1,3,5-TMPOH):0.667SiO 2:0.333GeO 2:0.025TiO 2:2HF:12H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于175℃烘箱中晶化144小时。反应后固体经过滤、洗涤、干燥、焙烧后得到的固体为含钛分子筛，XRD图谱与图2类似，产物中(Si+Ge)/Ti＝41。
Figure PCTCN2020100969-appb-000030
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。
【实施例11】
将4g氧化锗、5g白炭黑、0.145g硼酸溶于90.4g 1,1,3,5-TMPOH水溶液中(20wt％)，缓慢滴加0.59g钛酸四丁酯，水解完全后将容器敞口搅拌过夜以挥发丁醇和部分水，加入23.5g氟化铵溶液(37wt％)，搅拌均匀后继续挥发部分水，直到反应混合物达到以下摩尔组成：
1(1,1,3,5-TMPOH):0.667SiO 2:0.333GeO 2:0.01B 2O 3:0.015TiO 2:2NH 4F: 9.5H 2O
将上述混合物装入带有聚四氟乙烯内衬的晶化釜中，置于180℃烘箱中晶化168小时。反应后固体经过滤、洗涤、干燥、焙烧后得到的固体为含硼、钛分子筛，XRD图谱与图2类似，产物中(Si+Ge)/B＝55、(Si+Ge)/Ti＝60。
Figure PCTCN2020100969-appb-000031
焙烧前样品原位焙烧后得到的产物的XRD图谱的特征数据以及计算得到的晶面间距数据如上表所示。

Claims (18)

  1. 一种分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
    2θ(°) 6.53±0.3 7.05±0.3 9.56±0.3 10.77±0.3 12.84±0.3 18.80±0.3 22.60±0.3
    优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
    2θ(°) 7.81±0.3 14.37±0.3 14.76±0.3 15.45±0.3 16.35±0.3 17.52±0.3 19.79±0.3
    更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
    2θ(°) 21.46±0.3 22.04±0.3 23.64±0.3 24.54±0.3 25.14±0.3 26.11±0.3。
  2. 权利要求1的分子筛，其中所述分子筛是基于硅和锗的。
  3. 前述权利要求中任一项的分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
    Figure PCTCN2020100969-appb-100001
    Figure PCTCN2020100969-appb-100002
    优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
    Figure PCTCN2020100969-appb-100003
    更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
    Figure PCTCN2020100969-appb-100004
  4. 前述权利要求中任一项的分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
    2θ(°) 6.53±0.15 7.05±0.15 9.56±0.15 10.77±0.15 12.84±0.15 18.80±0.15 22.60±0.15
    优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
    2θ(°) 7.81±0.15 14.37±0.15 14.76±0.15 15.45±0.15 16.35±0.15 17.52±0.15 19.79±0.15
    更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
    2θ(°) 21.46±0.15 22.04±0.15 23.64±0.15 24.54±0.15 25.14±0.15 26.11±0.15。
  5. 前述权利要求中任一项的分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
    2θ(°) 相对强度(I/I 0)×100 6.53±0.15 m或s 7.05±0.15 vs 9.56±0.15 w或m 10.77±0.15 s 12.84±0.15 w或m 18.80±0.15 m或s 22.60±0.15 m或s
    优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
    2θ(°) 相对强度(I/I 0)×100 7.81±0.15 w 14.37±0.15 w 14.76±0.15 w 15.45±0.15 w
    16.35±0.15 w 17.52±0.15 w 19.79±0.15 w
    更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
    2θ(°) 相对强度(I/I 0)×100 21.46±0.15 w或m 22.04±0.15 w或m 23.64±0.15 m 24.54±0.15 m 25.14±0.15 m 26.11±0.15 w或m。
  6. 前述权利要求中任一项的分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
    2θ(°) 6.995±0.200 10.730±0.200 22.515±0.200 6.505±0.200 18.755±0.200
    优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
    2θ(°) 23.585±0.200 24.470±0.200 25.065±0.200 21.980±0.200 7.870±0.200 9.560±0.200
    更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
    2θ(°) 12.845±0.200 14.320±0.200 14.725±0.200
    15.380±0.200 16.295±0.200 17.490±0.200 19.745±0.200 21.400±0.200 26.055±0.200。
  7. 前述权利要求中任一项的分子筛，所述分子筛具有基本上如下表所示的X射线衍射图谱：
    2θ(°) 相对强度 6.995±0.200 vs 10.730±0.200 s 22.515±0.200 s 6.505±0.200 m或s 18.755±0.200 m或s
    优选地，所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰：
    2θ(°) 相对强度 23.585±0.200 m 24.470±0.200 m 25.065±0.200 m 21.980±0.200 w或m 7.870±0.200 w 9.560±0.200 w
    更优选地，所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰，
    2θ(°) 相对强度 12.845±0.200 w 14.320±0.200 w 14.725±0.200 w 15.380±0.200 w 16.295±0.200 w 17.490±0.200 w 19.745±0.200 w 21.400±0.200 w 26.055±0.200 w。
  8. 前述权利要求中任一项的分子筛，其特征在于，所述分子筛焙烧后的形式中具有如式“SiO 2·1/n GeO 2”所示的示意性化学组成，其中硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5。
  9. 前述权利要求中任一项的分子筛，其特征在于，所述分子筛合成态的形式中具有如式“kF·mQ·SiO 2·1/nGeO 2·pH 2O”所示的示意性化学组成，其中，
    硅锗摩尔比0.1≤n≤30，优选0.25≤n≤20，更优选0.5≤n≤15，更优选1≤n≤5；
    0.05≤k≤1.0，优选0.05≤k≤0.5，更优选0.1≤k≤0.5，更优选0.1≤k≤0.4；
    Q为有机模板剂，0.01≤m≤1.0，优选0.02≤m≤0.5，更优选0.05≤m≤0.5，更优选0.05≤m≤0.3；所述有机模板剂选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物；
    Figure PCTCN2020100969-appb-100005
    在上式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3，X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧根离子(OH -)；
    0.005≤p≤0.5，优选0.01≤p≤0.4，更优选0.01≤p≤0.3，更优选0.02≤p≤0.2。
  10. 前述权利要求中任一项的分子筛，其特征在于，所述分子筛中不超过10％的Ge原子被至少一种非硅和锗的元素的原子取代。
  11. 前述权利要求中任一项的分子筛，其特征在于，所述非硅和锗的元素选自由硼、铝、镓、钛、锆、铪、锡、锌、铁、铬和铟组成的组中的至少一种，优选选自由铝和钛组成的组中的至少一种。
  12. 一种分子筛的制备方法，包括将包含硅源、锗源、氟源、有机模板剂Q和水或者由硅源、锗源、氟源、有机模板剂Q和水形成的混合物晶化以获得所述分子筛的步骤；和任选地，焙烧所述获得的分子筛的步骤；
    其中所述有机模板剂Q选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式，优选1,1,3,5-四甲基哌啶氢氧化物；
    Figure PCTCN2020100969-appb-100006
    在式中，R 1-R 4各自独立地为H或者C 1-4烷基，优选C 1-2烷基，更优选-CH 3，X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -)，优选氢氧根离子(OH -)。
  13. 根据权利要求12所述分子筛的合成方法，其特征在于，所述硅源选自由水玻璃、硅溶胶、固体硅胶、气相白炭黑、无定形二氧化硅、硅藻土、沸石、正硅酸四乙酯组成的组中的至少一种；所述锗源选自由氧化锗、硝酸锗和四烷氧基锗组成的组中的至少一种，其中烷氧基是C 1-C 6烷氧基；
    所述有机模板剂Q、所述硅源(以SiO 2为计)、所述锗源(以GeO 2为计)、所述氟源(以F为计)和水的摩尔比为Q:SiO 2:GeO 2:F:H 2O＝0.15-4:1:0.033-10:0.2-4:0.5-50，优选Q:SiO 2:GeO 2:F:H 2O＝0.25-3.5:1:0.05-4:0.35-3.5:1-35，更优选Q:SiO 2:GeO 2:F:H 2O＝0.3-2.5:1:0.067-2:0.4-2.5:1.5-25，更优选Q:SiO 2:GeO 2:F:H 2O＝0.35-1.5:1:0.2-1:0.45-2:2-15。
  14. 根据权利要求12所述分子筛的合成方法，其特征在于，所述氟源包括选自由氢氟酸、氟化铵、氟化钠、氟化钾组成的组中的至少一种，优选为氢氟酸、氟化铵组成的组中的至少一种。
  15. 根据权利要求12所述的分子筛的合成方法，其特征在于，所述晶化条件包括在100-200℃晶化30-400小时；优选110-190℃晶化48-360小时；更优选120-180℃晶化72-320小时。
  16. 根据权利要求12所述分子筛的合成方法，其特征在于，所述混合物中还包括含非硅和锗的元素源，优选选自由硼源、铝源、镓源、钛源、锆源、铪源、锡源、锌源、铁源、铬源和铟源组成的组中的至少一种；更优选选自由氧化硼源、氧化铝源、氧化镓源、氧化钛源、氧化锆源、氧化铪源、氧化锡源、氧化锌源、氧化铁源、氧化铬源和氧化铟源组成的组中的至少一种氧化物源；
    所述氧化物源(以相应的氧化物为计)与所述锗源(以GeO 2为计)的摩尔比为(0.01-0.1):1，优选(0.015-0.08):1。
  17. 一种分子筛组合物，包含权利要求1至11任一所述的分子筛或者按照权利要求12至16任一所述分子筛的合成方法合成的分子筛，以及粘结剂。
  18. 权利要求1至11任一所述的分子筛、按照权利要求12至16任一所 述分子筛的合成方法合成的分子筛、或者权利要求17所述分子筛组合物作为吸附剂或催化剂的应用。
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