CN114180594B - Preparation method of ITH molecular sieve - Google Patents
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- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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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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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The invention discloses a preparation method of an ITH molecular sieve. The method comprises the following steps: mixing a silicon source, a germanium source, a fluorine source, an organic template agent Q, water and an optional heteroatom element X source, and performing crystallization reaction to obtain an ITH molecular sieve; wherein the organic template agent Q is N-ethyl-2-aminomethylpyrrolidine. The method adopts a low-cost organic template agent, the Si/Ge molar ratio can be adjusted in a wider area, and the synthesis steps are simple, the operability is strong, and the synthesis range is wide.
Description
Technical Field
The invention relates to the field of molecular sieve preparation, in particular to a preparation method of an ITH zeolite molecular sieve.
Background
Microporous molecular sieves are widely used in the fields of adsorption, separation, ion exchange, catalysis, etc., due to their regular pore structure and nanoscale pore size. The ITH structured molecular sieves possess a three-dimensional cross-channel system, parallel to [100 ]]The nine-membered ring pore path of the face is of the size ofParallel to [001 ]]The size of the ten-membered ring sinusoidal pore canal of the face is +.>Parallel to [010 ]]The size of the ten-membered ring straight pore canal of the face is +.>The ITH molecular sieve can be applied to hydrocarbon selective conversion processes, such as propylene generation by petroleum catalytic cracking, aromatic hydrocarbon compound conversion and the like, and has good application prospects in industry (J.Catal.2006, 238, 79-87).
ITH molecular sieves were originally reported by the A.Corma research group (US 6471941), the template agent used for synthesis was hexamethyl diammonium hydroxide, and the Si/Ge molar ratio in the raw materials was 6 to infinity. The template agent has high price and improves the synthesis cost. In addition to hexamethyldiammonium hydroxide, two templates have been reported for the synthesis of ITH molecular sieves. CN106698456a discloses a one-step synthesis method of aluminum-containing ITH molecular sieve using linear polyquaternary ammonium base organic template. The linear polyquaternary ammonium base is prepared by reacting 1, 4-dibromobutane with N, N, N, N-tetramethyl-1, 6-hexamethylenediamine under reflux condition, and performing recrystallization separation and ion exchange. It can be seen that the preparation process of the polyquaternary ammonium hydroxide is complex, the polymerization degree is not easy to control, and the preparation cost of the ITH molecular sieve is increased and the experimental reproducibility is not ideal. CN102502683a discloses a method for preparing an ITH molecular sieve in a non-concentrated gel system using N, N-tetramethyl-1, 6-hexamethylenediamine as a template. Compared with hexamethyldiammonium hydroxide, the template agent has lower price; however, the synthesis can only be carried out under the condition of rich germanium (Si/Ge is less than or equal to 1 and less than or equal to 4), the synthesis phase area is narrow, and excessive germanium in the product framework can cause the acidity and thermal stability of the ITH molecular sieve to be reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an ITH molecular sieve, which adopts a specific organic template agent, and has the advantages of simple operation, wide synthesis range and low price.
The first aspect of the present invention provides a method for preparing an ITH molecular sieve, comprising: mixing a silicon source, a germanium source, a fluorine source, an organic template agent Q, water and an optional heteroatom element X source, and performing crystallization reaction to obtain an ITH molecular sieve; and optionally, a step of calcining the molecular sieve; wherein the organic template agent Q is N-ethyl-2-aminomethylpyrrolidine.
Further, the structural formula of the organic template agent Q is shown as follows:
further, the heteroatom element X is at least one selected from aluminum, boron, gallium, titanium, zirconium, hafnium, tin, zinc, iron, indium, chromium, preferably at least one of aluminum and titanium.
Further, the organic template agent Q and the silicon source are prepared by SiO 2 For calculating, the germanium source is GeO 2 Meter, the X source is X 2 O m The molar ratio of the fluorine source to water is Q:SiO based on F 2 :GeO 2 :X 2 O m :F:H 2 O=0.15 to 4:1:0.02 to 1:0 to 0.1:0.2 to 4:0.5 to 25, preferably Q: siO 2 :GeO 2 :X 2 O m :F:H 2 O=0.35-1.5:1:0.04-0.2:0.005-0.05:0.45-2:2.5-15, wherein m is the oxidation state of the element X, and m=1-7.
Further, the silicon source is at least one selected from water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomite, zeolite molecular sieve and tetraalkoxysilane; the germanium source is selected from at least one of germanium oxide, germanium nitrate and tetraalkoxy germane; the fluorine source is at least one selected from hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride, preferably at least one selected from hydrofluoric acid and ammonium fluoride.
Further, the heteroatom element X source is at least one of an aluminum source, a boron source, a gallium source, a titanium source, a zirconium source, a hafnium source, a tin source, a zinc source, an iron source, an indium source and a chromium source; wherein the aluminum source is at least one selected from aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum chloride, pseudo-boehmite, aluminum oxide, aluminum hydroxide, aluminosilicate zeolite molecular sieve, aluminum carbonate, elemental aluminum, aluminum isopropoxide and aluminum acetate; the boron source is at least one selected from boric acid, sodium tetraborate, amorphous boron oxide, potassium borate, sodium metaborate, ammonium tetraborate and organic boron ester; the titanium source is selected from at least one of tetraalkyl titanate (such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra-n-butyl titanate), titanium tetrachloride, hexafluorotitanic acid, titanium sulfate and hydrolysate thereof; the tin source is at least one selected from tin tetrachloride, stannous chloride, alkyl tin, alkoxy tin and organic stannate; the iron source is at least one selected from ferric sulfate, ferric nitrate, ferric halide (such as ferric trichloride), ferrocene and ferric citrate; the gallium source, zirconium source, hafnium source, zinc source, indium source, chromium source are selected from the group of substances common in the art, such as gallium oxide, gallium nitrate, zirconium oxychloride, hafnium sulfate, zinc halide, zinc acetate, indium oxide, indium nitrate, chromium chloride, chromium nitrate, etc.
Further, the crystallization conditions include: crystallizing at 100-200 deg.c for 30-360 hr; preferably at 110 to 190 ℃ for 40 to 270 hours.
Further, after the crystallization reaction is finished, conventional post-treatment is carried out, such as the steps of filtering, washing and drying to prepare the molecular sieve; and optionally, a step of calcining the obtained molecular sieve.
In a second aspect, the present invention provides an ITH molecular sieve prepared by the above method, the ITH molecular sieve having the formula "SiO 2 ·1/x GeO 2 ·1/y X 2 O m "schematic chemical composition shown in the specification, wherein X is a heteroatom element, m is the oxidation state of the X element, m=1 to 7, siO 2 /GeO 2 The molar ratio of x is more than or equal to 1 and less than or equal to 50, preferably x is more than or equal to 5 and less than or equal to 25, and SiO 2 /X 2 O m The molar ratio y is more than or equal to 10.
The ITH molecular sieve has an X-ray diffraction pattern as shown in the following table:
in a third aspect the invention provides a molecular sieve composition comprising an ITH molecular sieve prepared according to the method of any preceding aspect, and a binder.
In a fourth aspect the present invention provides the use of a molecular sieve, an ITH molecular sieve prepared according to the method of any preceding aspect, or an ITH molecular sieve composition according to any preceding aspect, as an adsorbent or catalyst.
The preparation method of the ITH molecular sieve provided by the invention adopts a low-cost organic template agent, the Si/Ge molar ratio can be adjusted in a wider area, and the synthesis steps are simple, the operability is strong, and the synthesis range is wide; various elements such as Al, ti, zr, fe and the like can be introduced into the framework to generate different catalytic active centers, so that the requirements of different catalytic reactions are met, and the promotion is facilitated.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the sample obtained in example 1 after calcination;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the calcined sample obtained in example 1.
Detailed Description
In order to facilitate understanding of the present invention, the present invention is exemplified by the following examples. It will be apparent to those skilled in the art that the examples are merely to aid in the understanding of the present invention and should not be construed as a specific limitation thereof. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values.
In the context of this specification, vw, w, m, s, vs in the XRD data of the molecular sieve represents the diffraction peak intensity, vw is very weak, w is weak, m is medium, s is strong, vs is very strong, as is well known to those skilled in the art. Generally, vw is less than 5%; w is 5% -20%; m is 20% -40% (20%, 40%); s is 40% -70%; vs is greater than 70% (70% inclusive).
In the context of the present specification, the structure of a molecular sieve is determined by X-ray diffraction patterns (XRD) determined by an X-ray powder diffractometer using a Cu-ka radiation source, ka 1 wavelength λ= 1.5405980 angstromsA nickel filter.
In the invention, an X' Pert PRO X-ray powder diffraction (XRD) instrument of the Panac company of Netherlands is adopted, the working voltage is 40kV, the current is 40mA, and the scanning range is 5-40 degrees. The morphology of the product was photographed by a field emission scanning electron microscope (Fe-SEM) model S-4800 from HITACHI corporation of Japan.
It is specifically noted that two or more aspects (or embodiments) disclosed in the context of this specification may be arbitrarily combined with each other, and the resulting solution (such as a method or system) is part of the original disclosure of this specification, while also falling within the scope of the invention.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
[ example 1 ]
1.9g of germanium oxide was dissolved in 13g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 25g of water, 27.3g of Ludox-AS-40 silica sol was slowly added, stirred uniformly at room temperature, the vessel was left open to stir overnight to volatilize part of the water, 5g of hydrofluoric acid (40 wt%) was added, and after stirring uniformly, the volatilization of part of the water was continued until the reaction mixture reached the following molar composition:
0.5OSDA:0.909SiO 2 :0.091GeO 2 :0.5HF:7H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a baking oven at 170 ℃ for crystallization for 168 hours. The solid after reaction is filtered, washed by distilled water and dried at 100 ℃ to obtain the original powder ITH molecular sieve. The raw powder solid is put into a muffle furnace to be roasted for 6 hours at 550 ℃ to obtain the final product,the XRD patterns of the samples are shown in figure 1, the pattern data are shown in table 1, and the scanning electron microscope pictures are shown in figure 2. The obtained ITH molecular sieve has the formula of SiO 2 ·0.125GeO 2 "schematic chemical composition shown.
TABLE 1
[ example 2 ]
3g of germanium oxide was dissolved in 19.5g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 38g of water, 35.7g of tetraethyl orthosilicate (TEOS) was slowly added, stirred at room temperature, after hydrolysis was complete, the vessel was left open to stir overnight to volatilize ethanol and part of the water, 15g of ammonium fluoride solution (37 wt%) was added, and after stirring was uniform part of the water was continued to volatilize until the reaction mixture reached the following molar composition:
0.75OSDA:0.857SiO 2 :0.143GeO 2 :0.75NH 4 F:3H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 160 ℃ oven for crystallization for 240 hours. Filtering, washing, drying and calcining the reacted solid to obtain ITH molecular sieve, XRD pattern data are shown in Table 2, and the obtained ITH molecular sieve has the formula' SiO 2 ·0.2GeO 2 "schematic chemical composition shown.
TABLE 2
[ example 3 ]
2.5g of germanium oxide was dissolved in 10.4g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 20g of water, 26.4g of Ludox-AS-40 silica sol was slowly added, stirred uniformly at room temperature, the vessel was left open to stir overnight to volatilize part of the water, 5g of hydrofluoric acid (40 wt%) and 10g of ammonium fluoride solution (37 wt%) were added, and after stirring uniformly, the volatilization of part of the water was continued until the reaction mixture reached the following molar composition:
0.4OSDA:0.88SiO 2 :0.12GeO 2 :0.5HF:0.5NH 4 F:4.8H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 175 ℃ oven for crystallization for 144 hours. Filtering, washing, drying and calcining the reacted solid to obtain an ITH molecular sieve, wherein XRD pattern data are shown in table 3, and the obtained ITH molecular sieve has a formula of SiO 2 ·0.17GeO 2 "schematic chemical composition shown.
TABLE 3 Table 3
[ example 4 ]
1.4g of germanium oxide was dissolved in 26g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 50g of water, 38.8g of tetraethyl orthosilicate (TEOS) was slowly added, stirred at room temperature, after hydrolysis was completed, the vessel was left open to stir overnight to volatilize ethanol and part of the water, 12g of hydrofluoric acid (40 wt%) was added, and after stirring uniformly, the volatilization of part of the water was continued until the reaction mixture reached the following molar composition:
1OSDA:0.933SiO 2 :0.067GeO 2 :1.2HF:13.5H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a baking oven at 165 ℃ for crystallization for 216 hours. The solid after reaction is filtered, washed, dried and calcined to obtain the ITH molecular sieve, and the XRD pattern of the ITH molecular sieve is similar to that of figure 1. The obtained ITH molecular sieve has the formula of SiO 2 ·0.07GeO 2 "schematic chemical composition shown.
[ example 5 ]
1.04g of germanium oxide was dissolved in 32.5. 32.5g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 62.5g of water, 39.5g of tetraethyl orthosilicate (TEOS) was slowly added, stirred at room temperature, after hydrolysis was completed, the vessel was left open to stir overnight to volatilize ethanol and part of the water, 60g of ammonium fluoride solution (37 wt%) was added, and after stirring was uniform part of the water was continued until the reaction mixture reached the following molar composition:
1.25OSDA:0.95SiO 2 :0.05GeO 2 :3NH 4 F:16H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a baking oven at 150 ℃ for crystallization for 192 hours. Filtering, washing, drying and calcining the reacted solid to obtain an ITH molecular sieve, wherein XRD pattern data are shown in table 4, and the obtained ITH molecular sieve has a formula of SiO 2 ·0.05GeO 2 "schematic chemical composition shown.
TABLE 4 Table 4
[ example 6 ]
0.4g of aluminum isopropoxide, 1.9g of germanium oxide were dissolved in 13g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 25g of water, 27.3g of Ludox-AS-40 silica sol was slowly added and stirred uniformly at room temperature, the vessel was left open to stir overnight to volatilize propanol and part of the water, 10g of hydrofluoric acid (40 wt%) was added, and after stirring uniformly, the volatilization of part of the water was continued until the reaction mixture reached the following molar composition:
0.5OSDA:0.909SiO 2 :0.091GeO 2 :0.005Al 2 O 3 :1HF:5H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a baking oven at 165 ℃ for crystallization for 250 hours. The solid obtained after the reaction is filtered, washed, dried and calcined, and is an aluminum-containing ITH molecular sieve, and the XRD pattern of the solid is similar to that of figure 1. By a means ofThe obtained ITH molecular sieve has the formula of SiO 2 ·0.13GeO 2 ·0.003Al 2 O 3 "schematic chemical composition shown.
[ example 7 ]
1g of aluminum isopropoxide, 2.6g of germanium oxide were dissolved in 13g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 25g of water, 26.3g of Ludox-AS-40 silica sol was slowly added, stirred uniformly at room temperature, the vessel was left open to stir overnight to volatilize propanol and part of the water, 10g of hydrofluoric acid (40 wt%) and 10g of ammonium fluoride solution (37 wt%) were added, and after stirring uniformly part of the water was continued until the reaction mixture reached the following molar composition:
0.5OSDA:0.875SiO 2 :0.125GeO 2 :0.0125Al 2 O 3 :1HF:0.5NH 4 F:8H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 155 ℃ oven for crystallization for 300 hours. The solid obtained after the reaction is filtered, washed, dried and calcined, and is an aluminum-containing ITH molecular sieve, and the XRD pattern of the solid is similar to that of figure 1. The obtained ITH molecular sieve has the formula of SiO 2 ·0.15GeO 2 ·0.009Al 2 O 3 "schematic chemical composition shown.
[ example 8 ]
1.67g germanium oxide was dissolved in 15.6g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 30g water, and 16.6g Ludox-AS-40 silica sol and 4.6g USY molecular sieve (SiO 2 /Al 2 O 3 After completion of hydrolysis the vessel was left open to stir overnight to volatilize part of the water, 28g of ammonium fluoride solution (37 wt%) was added and after stirring well part of the water was continued to volatilize until the reaction mixture reached the following molar composition:
0.6OSDA:0.92SiO 2 :0.08GeO 2 :0.01Al 2 O 3 :1.4NH 4 F:11H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 185 ℃ oven for crystallization for 168 hours. The solid obtained after the reaction is filtered, washed, dried and calcined, and is an aluminum-containing ITH molecular sieve, and the XRD pattern of the solid is similar to that of figure 1. By a means ofThe obtained ITH molecular sieve has the formula of SiO 2 ·0.12GeO 2 ·0.007Al 2 O 3 "schematic chemical composition shown.
[ example 9 ]
2.1g of germanium oxide was dissolved in 13g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 25g of water, 37.4g of tetraethyl orthosilicate (TEOS) was slowly added, after hydrolysis was complete, 2g of ferric nitrate nonahydrate was added, the vessel was left open to stir overnight to volatilize ethanol and part of the water, 5g of hydrofluoric acid (40 wt%) and 30g of ammonium fluoride solution (37 wt%) were added, and after stirring uniformly part of the water was continued until the reaction mixture reached the following molar composition:
0.5OSDA:0.9SiO 2 :0.1GeO 2 :0.0125Fe 2 O 3 :0.5HF:1.5NH 4 F:6.6H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a drying oven at 145 ℃ for crystallization for 192 hours. The solid obtained after the reaction is filtered, washed, dried and calcined is an iron-containing ITH molecular sieve, and the XRD pattern of the solid is similar to that of figure 1. The obtained ITH molecular sieve has the formula of SiO 2 ·0.13GeO 2 ·0.008Fe 2 O 3 "schematic chemical composition shown.
[ example 10 ]
2.1g of germanium oxide is dissolved in 20.8-g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 40g of water, 37.4g of tetraethyl orthosilicate (TEOS) is slowly added, after being uniformly stirred, 0.85g of tetrabutyl titanate is slowly added dropwise, the mixture is stirred at normal temperature, after the hydrolysis is completed, the container is opened and stirred overnight to volatilize ethanol, butanol and part of water, 20g of hydrofluoric acid (40 wt%) is added, and after being uniformly stirred, part of water is continuously volatilized until the reaction mixture reaches the following molar composition:
0.8OSDA:0.9SiO 2 :0.1GeO 2 :0.0125TiO 2 :2HF:12H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 175 ℃ oven for crystallization for 144 hours. The solid obtained by filtering, washing, drying and calcining the reacted solid is a titanium-containing ITH molecular sieve, XRD pattern data are shown in Table 5The ITH molecular sieve obtained has the formula' SiO 2 ·0.12GeO 2 ·0.012TiO 2 "schematic chemical composition shown.
TABLE 5
[ example 11 ]
2.1g of germanium oxide, 11.4g of white carbon black, 0.125g of boric acid are dissolved in 19.5g N-ethyl-2-aminomethylpyrrolidine (OSDA) and 37.5g of water, 1g of tetrabutyl titanate is slowly added dropwise, after the hydrolysis is completed, the container is left open to stir overnight to volatilize butanol and part of water, 40g of ammonium fluoride solution (37 wt%) is added, and after stirring uniformly, the volatilization of part of water is continued until the reaction mixture reaches the following molar composition:
0.75OSDA:0.9SiO 2 :0.1GeO 2 :0.005B 2 O 3 :0.015TiO 2 :2NH 4 F:9.5H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 180 ℃ oven for crystallization for 168 hours. The solid obtained after the reaction is filtered, washed, dried and calcined is a boron-containing and titanium ITH molecular sieve, and the XRD pattern of the solid is similar to that of figure 1. The obtained ITH molecular sieve has the formula of SiO 2 ·0.11GeO 2 ·0.01TiO 2 ·0.004B 2 O 3 "schematic chemical composition shown.
Claims (14)
1. A method for synthesizing an ITH zeolite molecular sieve is characterized in that: comprising the following steps: mixing a silicon source, a germanium source, a fluorine source, an organic template agent Q, water and an optional heteroatom element X source, and performing crystallization reaction to obtain an ITH molecular sieve; and optionally, a step of calcining the molecular sieve; wherein the organic template agent Q is N-ethyl-2-aminomethylpyrrolidine.
2. A method according to claim 1, characterized in that: the heteroatom element X is at least one selected from aluminum, boron, gallium, titanium, zirconium, hafnium, tin, zinc, iron, indium and chromium.
3. A method according to claim 2, characterized in that: the heteroatom element X is at least one of aluminum and titanium.
4. A method according to claim 1, characterized in that: the organic template agent Q and the silicon source are prepared from SiO 2 Meter, the germanium source is GeO 2 Meter, the X source is X 2 O m The molar ratio of the fluorine source to water is Q:SiO based on F 2 :GeO 2 :X 2 O m :F:H 2 O=0.15~4:1:0.02~1:0~0.1:0.2~4:0.5~25。
5. A method according to claim 1, characterized in that: the organic template agent Q and the silicon source are prepared from SiO 2 Meter, the germanium source is GeO 2 Meter, the X source is X 2 O m The molar ratio of the fluorine source to water is Q:SiO based on F 2 :GeO 2 :X 2 O m :F:H 2 O=0.35-1.5:1:0.04-0.2:0.005-0.05:0.45-2:2.5-15, wherein m is the oxidation state of the element X, and m=1-7.
6. A method according to claim 1, characterized in that: the silicon source is at least one selected from water glass, silica sol, solid silica gel, gas-phase white carbon black, amorphous silica, diatomite, zeolite molecular sieve and tetraalkoxysilane; the germanium source is selected from at least one of germanium oxide, germanium nitrate and tetraalkoxy germane; the fluorine source is at least one selected from hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride.
7. The method of claim 6, wherein: the fluorine source is at least one selected from hydrofluoric acid and ammonium fluoride.
8. A method according to claim 1, characterized in that: the crystallization conditions include: crystallizing at 100-200 deg.c for 30-360 hr.
10. an ITH molecular sieve prepared according to any one of claims 1 to 9, characterised in that: the ITH molecular sieve has the formula of SiO 2 ·1/x GeO 2 ·1/y X 2 O m "schematic chemical composition shown in the specification, wherein X is a heteroatom element, m is the oxidation state of the X element, m=1 to 7, siO 2 /GeO 2 The mol ratio of x is more than or equal to 1 and less than or equal to 50, siO 2 /X 2 O m The molar ratio y is more than or equal to 10.
11. The ITH molecular sieve according to claim 10, wherein: siO (SiO) 2 /GeO 2 The molar ratio of x is more than or equal to 5 and less than or equal to 25.
13. a molecular sieve composition characterized by: comprising an ITH molecular sieve prepared by the method according to any one of claims 1 to 9 or an ITH molecular sieve according to any one of claims 10 to 12, and a binder.
14. Use of an ITH molecular sieve prepared according to any one of claims 1 to 9 or an ITH molecular sieve according to any one of claims 10 to 12 or a molecular sieve composition according to claim 13 as an adsorbent or catalyst.
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