CN114180595B - ITQ-26 molecular sieve and preparation method thereof - Google Patents

ITQ-26 molecular sieve and preparation method thereof Download PDF

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CN114180595B
CN114180595B CN202010960858.8A CN202010960858A CN114180595B CN 114180595 B CN114180595 B CN 114180595B CN 202010960858 A CN202010960858 A CN 202010960858A CN 114180595 B CN114180595 B CN 114180595B
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molecular sieve
itq
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germanium
sio
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CN114180595A (en
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付文华
王振东
袁志庆
陶伟川
刘松霖
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention discloses an ITQ-26 molecular sieve and a preparation method thereof. The molar ratio of silicon to germanium of the ITQ-26 molecular sieve is 2-100; the specific surface area of the ITQ-26 molecular sieve is more than 600m 2 /g and/or external specific surface area greater than 100m 2 /g; the micropore volume of the ITQ-26 molecular sieve is 0.2cm 3 And/g. The preparation method of the ITQ-26 molecular sieve comprises the following steps: mixing silicon source, germanium source, fluorine source, organic template agent Q, water and any oneMixing the selected heteroatom element X sources, and performing crystallization reaction to obtain an ITQ-26 molecular sieve; wherein the organic template Q is selected from substances containing 1,3-bis (1-adamantyl) imidazolium ions. The ITQ-26 molecular sieve has higher silicon-germanium molar ratio, higher micropore volume and higher specific surface area, and the preparation method adopts a low-cost organic template agent, so that the ITQ-26 molecular sieve can be completely removed from pore channels through roasting.

Description

ITQ-26 molecular sieve and preparation method thereof
Technical Field
The invention relates to the field of molecular sieves, in particular to an ITQ-26 molecular sieve and a preparation method thereof.
Background
The zeolite molecular sieve is a porous crystalline material, has a regular molecular size pore structure, stronger acidity and high hydrothermal stability, is widely applied to the fields of catalysis, adsorption, ion exchange and the like, and plays an irreplaceable role. Currently, 252 molecular sieve topologies approved by the international molecular sieve association have been achieved.
The ITQ-26 molecular sieve is a silicon germanium molecular sieve and has a three-dimensional 12 multiplied by 12-membered ring opening pore canal structure. The ITQ-26 molecular sieve open pore system has a great application prospect in the fields of adsorption separation, organic catalytic conversion and the like. ITQ-26 molecular sieves were first synthesized by Corma et al, university of Spanish, barenia (WO 20070753832A 1, chem. Mater.2008,20, 5325-5331), the templating agent used was a quaternary phosphonium salt, 1,3-bis- (triethylphosphinummethyl) -benzene dihydroxide, the silicon germanium mole in the productThe ratio Si/ge=4. Quaternary phosphonium salts are an important class of organic structure directing agents for the synthesis of molecular sieves and can be used to prepare a variety of molecular sieves, including ITQ-27 (WO 2006055305 A2), ITQ-40 (WO 2011081982 A2), ITQ-34 (WO 2008073237 A2), and the like. However, such templating agents are generally not commercially available and are relatively expensive; calcination of the synthesized molecular sieve product to produce pH 3 The highly toxic gas, part of P element is deposited in the form of phosphorus oxide and is blocked in the pore canal, so that the P element cannot be completely removed.
The university of south Beijing Du Gongbin professor ed that the template was completely removed by calcination, a novel method for synthesizing ITQ-26 molecular sieves using the imidazole derivative 1,2-dimethyl-3- (2-fluoroxynzyl) imidazolium or 1-methyl-3- (2-fluoroxynzyl) -imidazolium. However, the ITQ-26 molecular sieve synthesized by the method has too high germanium content (Si/Ge=0.5-1), and the hydrothermal stability of the molecular sieve is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an ITQ-26 molecular sieve and a preparation method thereof, wherein the ITQ-26 molecular sieve has higher silicon-germanium molar ratio, higher micropore volume and higher specific surface area, and the preparation method adopts a low-cost organic template agent, so that the ITQ-26 molecular sieve can be completely removed from a pore canal through roasting.
In a first aspect of the invention, there is provided an ITQ-26 molecular sieve having a silicon to germanium molar ratio of from 2 to 100, preferably from 5 to 25.
The specific surface area of the ITQ-26 molecular sieve is more than 600m 2 /g, preferably 700m 2 /g～1000m 2 /g, and/or an external specific surface area of greater than 100m 2 /g, preferably 120m 2 /g～180m 2 /g。
The micropore volume of the ITQ-26 molecular sieve is 0.2cm 3 Preferably 0.24 to 0.30cm per gram 3 /g。
Further, the ITQ-26 molecular sieve is a rod-shaped crystal, the length is 300-600 nm, and the section diameter is 50-150 nm.
Further, the ITQ-26 molecular sieve has 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 2 and less than or equal to 100, 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 ITQ-26 molecular sieve has an X-ray diffraction pattern as shown in the following table:
in a second aspect of the present invention, there is provided a process for preparing an ITQ-26 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 ITQ-26 molecular sieve; wherein the organic template Q is selected from substances containing 1,3-bis (1-adamantyl) imidazolium ions.
Further, the structural formula of the 1,3-bis (1-adamantyl) imidazolium ion is as follows:
further, the organic template Q is preferably a hydroxide containing 1,3-bis (1-adamantyl) imidazolium ion, such as 1,3-bis (1-adamantyl) imidazole hydroxide (or 1,3-bis (1-adamantyl) imidazolium hydroxide, or abbreviated as BAdaImOH).
Further, the heteroatom element X is at least one selected from aluminum, boron, gallium, titanium, zirconium, hafnium, tin, zinc, iron, indium and chromium.
Further, the organic template agent Q and the silicon source are prepared by 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 to 4:1:0.01 to 0.5:0 to 0.1:0.2 to 4:0.5 to 30; preferably Q: siO 2 :GeO 2 :X 2 O m :F:H 2 O=0.3 to 1.5:1:0.04 to 0.2:0.005 to 0.05:0.35 to 2.5:5 to 15, wherein m is the oxidation state of the element X, and m=1 to 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.
Further, the germanium source is selected from at least one of germanium oxide, germanium nitrate, and tetraalkoxy germanium.
Further, 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 72-720 hr; preferably at 110-190 deg.c for 120-360 hr.
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 third aspect the present invention provides a molecular sieve composition comprising an ITQ-26 molecular sieve according to any preceding aspect or an ITQ-26 molecular sieve prepared by any of the methods described herein, and a binder.
In a fourth aspect, the present invention provides the use of a molecular sieve, an ITQ-26 molecular sieve according to any preceding aspect, or an ITQ-26 molecular sieve prepared according to any preceding aspect, or an ITQ-26 molecular sieve composition according to any preceding aspect, as an adsorbent or catalyst.
The ITQ-26 molecular sieve provided by the invention has lower germanium content and larger specific surface area and micropore volume.
The method for preparing the ITQ-26 molecular sieve provided by the invention adopts the imidazolyl quaternary ammonium salt organic template agent, so that the synthesis cost is reduced; the organic template agent can be completely removed during roasting, so that the pore canal is completely exposed; the synthesis range is wide, and the operation is simple; and a plurality of 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 industrial popularization is facilitated.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the final sample obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the final sample obtained in example 1;
FIG. 3 is a nitrogen adsorption/desorption isotherm of the final sample obtained in example 1;
FIG. 4 is an X-ray diffraction (XRD) pattern of the final sample obtained in example 2;
fig. 5 is a Scanning Electron Microscope (SEM) photograph of the final sample obtained in example 2.
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. Nitrogen adsorption was measured using a Quadraorb evo type capacity physisorption instrument from Quantachrome, inc., USA at a test temperature of 77K. The specific surface area of the molecular sieve is calculated by adopting a BET (Brunauer-Emmett-Teller) method, and the external specific surface area and the micropore volume are calculated by adopting a t-Plot method.
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 ]
0.52g of germanium oxide was dissolved in 88.5g of an aqueous solution of 1,3-bis (1-adamantyl) imidazole hydroxide (BAdaImOH, 20 wt%) and 19.8g of tetraethyl orthosilicate was slowly added, stirred at room temperature, after the hydrolysis was completed, the vessel was left open to stir overnight to volatilize ethanol and part of the water, 2.5g of hydrofluoric acid (40 wt%) was added, and after stirring was uniform, the volatilization of part of the water was continued until the reaction mixture reached the following molar composition:
0.5BAdaImOH:0.95SiO 2 :0.05GeO 2 :0.5HF:5H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 175 ℃ oven for crystallization for 168 hours. The solid after reaction is filtered, washed by distilled water and dried at 100 ℃ to obtain the original powder ITQ-26 molecular sieve. And (3) placing the raw powder solid in a muffle furnace and roasting for 6 hours at 550 ℃ to obtain the final product. The obtained ITQ-26 molecular sieve has the formula of SiO 2 ·0.05GeO 2 "illustrative chemical composition shown, having a specific surface area of 698m 2 Per gram, external specific surface area of 140m 2 Per gram, micropore volume of 0.24cm 3 And/g, the obtained ITQ-26 molecular sieve is a rod-shaped crystal, the length is about 500nm, the cross-sectional diameter is about 100nm, the XRD pattern is shown in figure 1, the SEM picture is shown in figure 2, and the nitrogen adsorption and desorption isotherm is shown in figure 3. XRD spectrum data of the final product are shown in table 1:
TABLE 1
[ example 2 ]
0.95g of germanium oxide was dissolved in 88.5g of an aqueous solution of 1,3-bis (1-adamantyl) imidazole hydroxide (BAdaImOH, 20 wt%) and 18.9g of tetraethyl orthosilicate was slowly added, stirred at room temperature, after the hydrolysis was completed, the vessel was left open to stir overnight to volatilize ethanol and part of the water, 2.5g of hydrofluoric acid (40 wt%) was added, and after stirring was uniform, the volatilization of part of the water was continued until the reaction mixture reached the following molar composition:
0.5BAdaImOH:0.909SiO 2 :0.091GeO 2 :0.5HF:6H 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 240 hours. The solid obtained after the reaction is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1) is the ITQ-26 molecular sieve. The obtained ITQ-26 molecular sieve has the formula of SiO 2 ·0.1GeO 2 "illustrative chemical composition shown, having a specific surface area of 830m 2 Per gram, external specific surface area of 188m 2 Per gram, micropore volume of 0.27cm 3 And/g, the obtained ITQ-26 molecular sieve is a rod-shaped crystal, the length is about 550nm, the section diameter is about 80nm, the XRD pattern is shown in figure 4, the SEM picture is shown in figure 5, and the XRD pattern data of the final product are shown in Table 2:
TABLE 2
[ example 3 ]
1.57g of germanium oxide was dissolved in 115g of 1,3-bis (1-adamantyl) imidazole hydroxide aqueous solution (BAdaImOH, 20 wt%) 17.7g of tetraethyl orthosilicate 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, 6.5g 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:
0.65BAdaImOH:0.85SiO 2 :0.15GeO 2 :0.65NH 4 F:7.5H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 180 ℃ oven for crystallization for 216 hours. The solid obtained after the reaction is IT after the solid is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1)Q-26 molecular sieve. The obtained ITQ-26 molecular sieve has the formula of SiO 2 ·0.17GeO 2 "illustrative chemical composition shown, its specific surface area is 805m 2 Per gram, external specific surface area of 195m 2 Per gram, micropore volume of 0.25cm 3 And/g, the obtained ITQ-26 molecular sieve is a rod-shaped crystal, the length is about 480nm, the section diameter is about 75nm, the XRD pattern is similar to that of FIG. 1, and the XRD pattern data of the product are shown in Table 3:
TABLE 3 Table 3
[ example 4 ]
0.63g of germanium oxide was dissolved in 132.8g of an aqueous solution of 1,3-bis (1-adamantyl) imidazole hydroxide (BAdaImOH, 20 wt%) and 14.1g of Ludox-AS-40 silica sol (SiO 2 40 wt%) was stirred well and the vessel was left open to stir overnight to volatilize part of the water, 1.75g hydrofluoric acid (40 wt%) and 4g ammonium fluoride solution (37 wt%) were added and after stirring well the evaporation of part of the water was continued until the reaction mixture reached the following molar composition:
0.75BAdaImOH:0.94SiO 2 :0.06GeO 2 :0.35HF:0.4NH 4 F:8.5H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 160 ℃ oven for crystallization for 192 hours. The solid obtained after the reaction is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1) is ITQ-26 molecular sieve, and the obtained ITQ-26 molecular sieve has the following formula of SiO 2 ·0.062GeO 2 "illustrative chemical composition shown, having a specific surface area of 644m 2 Per gram, external specific surface area 122m 2 Per gram, micropore volume of 0.25cm 3 The ITQ-26 molecular sieve obtained was a rod-like crystal having a length of about 520nm and a cross-sectional diameter of about 125nm, and its XRD pattern was similar to that of FIG. 1.
[ example 5 ]
0.95g of germanium oxide was dissolved in 88.5g of an aqueous solution of 1,3-bis (1-adamantyl) imidazole hydroxide (BAdaImOH, 20 wt%) 18.9g of tetraethyl orthosilicate and 0.41g of aluminum isopropoxide were slowly added and stirred at room temperature, after the hydrolysis was completed the vessel was left open to stir overnight to volatilize ethanol, isopropanol and part of the water, 3g of hydrofluoric acid (40 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:
0.5BAdaImOH:0.909SiO 2 :0.091GeO 2 :0.01Al 2 O 3 :0.6HF:10H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 175 ℃ oven for crystallization for 288 hours. The solid obtained after the reaction is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1) is ITQ-26 molecular sieve, and the obtained ITQ-26 molecular sieve has the following formula of SiO 2 ·0.09·GeO 2 ·0.0083Al 2 O 3 "illustrative chemical composition shown, its specific surface area is 720m 2 Per gram, external specific surface area of 176m 2 Per gram, micropore volume of 0.24cm 3 And/g, the obtained ITQ-26 molecular sieve is a rod-shaped crystal, the length is about 420nm, the section diameter is about 120nm, the XRD pattern is similar to that of FIG. 1, and the XRD pattern data of the product are shown in Table 4:
TABLE 4 Table 4
[ example 6 ]
0.42g germanium oxide was dissolved in 70.8g 1,3-bis (1-adamantyl) imidazole hydroxide aqueous solution (BAdaImOH, 20 wt%) and 4.55g white carbon black (SiO) 2 95 wt%) and 1.64g of USY molecular sieve (SiO 2 /Al 2 O 3 ) Stirring the container at room temperature overnight to volatilize part of water, adding2.5g of hydrofluoric acid (40% by weight) and 5g of ammonium fluoride solution (37% by weight) were added, after stirring well, the evaporation of part of the water was continued until the reaction mixture reached the following molar composition:
0.4BAdaImOH:0.96SiO 2 :0.04GeO 2 :0.02Al 2 O 3 :0.5HF:0.5NH 4 F:12H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 185 ℃ oven for crystallization for 300 hours. The solid obtained after the reaction is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1) is ITQ-26 molecular sieve, and the obtained ITQ-26 molecular sieve has the following formula of SiO 2 ·0.04·GeO 2 ·0.02Al 2 O 3 "illustrative chemical composition shown, having a specific surface area of 681m 2 Per gram, external specific surface area of 160m 2 Per gram, micropore volume of 0.23cm 3 The ITQ-26 molecular sieve obtained was a rod-like crystal having a length of about 380nm and a cross-sectional diameter of about 135nm, and its XRD pattern was similar to that of FIG. 1.
[ example 7 ]
0.52g of germanium oxide and 1.62g of ferric nitrate nonahydrate are dissolved in 88.5g of 1,3-bis (1-adamantyl) imidazole hydroxide aqueous solution (BAdaImOH, 20 wt%) and 19.8g of tetraethyl orthosilicate are slowly added, stirred at normal temperature, after hydrolysis is completed, the container is left open to stir overnight to volatilize ethanol and part of water, 6g of ammonium fluoride solution (37 wt%) is added, and after stirring uniformly part of water is continuously volatilized until the reaction mixture reaches the following molar composition:
0.5BAdaImOH:0.95SiO 2 :0.05GeO 2 :0.02Fe 2 O 3 :0.6NH 4 F:8.8H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 160 ℃ oven for crystallization for 144 hours. The solid obtained after the reaction is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1) is ITQ-26 molecular sieve, and the obtained ITQ-26 molecular sieve has the following formula of SiO 2 ·0.048·GeO 2 ·0.016Fe 2 O 3 "illustrative chemical composition shown, having a specific surface area of 620m 2 Per gram, external specific surface area of 108m 2 Per gram, micropore volume of 0.21cm 3 The ITQ-26 molecular sieve obtained was a rod-like crystal having a length of about 560nm and a cross-sectional diameter of about 125nm, and its XRD pattern was similar to that of FIG. 1.
[ example 8 ]
0.52g of germanium oxide was dissolved in 88.5g of an aqueous solution of 1,3-bis (1-adamantyl) imidazole hydroxide (BAdaImOH, 20 wt%) and 19.8g of tetraethyl orthosilicate and 0.425g of tetrabutyl titanate were slowly added and stirred at room temperature, after the hydrolysis was completed, the vessel was left open to stir overnight to volatilize ethanol, butanol and part of the water, 4g of hydrofluoric acid (40 wt%) was added, and after stirring was uniform, the volatilization of part of the water was continued until the reaction mixture reached the following molar composition:
0.5BAdaImOH:0.95SiO 2 :0.05GeO 2 :0.0125TiO 2 :0.8HF:7H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 180 ℃ oven for crystallization for 216 hours. The solid obtained after the reaction is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1) is ITQ-26 molecular sieve, and the obtained ITQ-26 molecular sieve has the following formula of SiO 2 ·0.047·GeO 2 ·0.01TiO 2 "illustrative chemical composition shown, having a specific surface area of 644m 2 Per gram, external specific surface area of 155m 2 Per gram, micropore volume of 0.23cm 3 And/g, the obtained ITQ-26 molecular sieve is a rod-shaped crystal, the length is about 490nm, the section diameter is about 110nm, the XRD pattern is similar to that of FIG. 1, and the XRD pattern data of the product are shown in Table 5:
TABLE 5
/>
[ example 9 ]
0.52g of germanium oxide and 0.124g of boric acid are dissolved in 97.4g of 1,3-bis (1-adamantyl) imidazole hydroxide aqueous solution (BAdaImOH, 20 wt%) and 19.8g of tetraethyl orthosilicate (TEOS) and 0.425g of tetrabutyl titanate are slowly added, stirring is carried out at normal temperature, after the hydrolysis is completed, the container is opened and stirred overnight to volatilize ethanol, butanol and part of water, 3g of hydrofluoric acid (40 wt%) and 3g of ammonium fluoride solution (37 wt%) are added, and after stirring, part of water is volatilized continuously until the reaction mixture reaches the following molar composition:
0.55BAdaImOH:0.95SiO 2 :0.05GeO 2 :0.01B 2 O 3 :0.0125TiO 2 :0.6HF:0.3NH 4 F:13.5H 2 O
the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and placed into a 185 ℃ oven for crystallization for 336 hours. The solid obtained after the reaction is filtered, washed, dried and baked (the post-treatment reaction condition is the same as that of the example 1) is ITQ-26 molecular sieve, and the obtained ITQ-26 molecular sieve has the following formula of SiO 2 ·0.048·GeO 2 ·0.009TiO 2 ·0.007B 2 O 3 "illustrative chemical composition shown, having a specific surface area of 625m 2 Per gram, external specific surface area 122m 2 Per gram, micropore volume of 0.23cm 3 The ITQ-26 molecular sieve obtained was a rod-like crystal having a length of about 510nm and a cross-sectional diameter of about 120nm, and its XRD pattern was similar to that of FIG. 1.

Claims (17)

1. An ITQ-26 molecular sieve, characterized by: the molar ratio of silicon to germanium of the molecular sieve is 5-25, and the specific surface area of the ITQ-26 molecular sieve is more than 600m 2 /g；
The micropore volume of the ITQ-26 molecular sieve is 0.2cm 3 /g or more; the ITQ-26 molecular sieve is a rod-shaped crystal, the length is 300-600 nm, and the section diameter is 50-150 nm.
2. The ITQ-26 molecular sieve of claim 1, wherein: the specific surface area of the ITQ-26 molecular sieve is 700m 2 /g~1000 m 2 /g, and/or an external specific surface area greater than 100m 2 /g。
3. The ITQ-26 molecular sieve of claim 2, wherein: the saidThe external specific surface area of the ITQ-26 molecular sieve is 120m 2 /g~180 m 2 /g。
4. The molecular sieve of claim 1, wherein: the micropore volume of the ITQ-26 molecular sieve is 0.24-0.30 cm 3 /g。
5. The molecular sieve of claim 1, wherein: the ITQ-26 molecular sieve has the formula of SiO 2 ·1/x GeO 2 ·1/y X 2 O m "illustrative chemical composition shown, wherein X is a heteroatom element,min the oxidation state of the element X,m=1~7，SiO 2 /GeO 2 the molar ratio of x is more than or equal to 5 and less than or equal to 25, siO 2 /X 2 O m The molar ratio y is more than or equal to 10.
6. The molecular sieve of claim 1, wherein: the ITQ-26 molecular sieve has an X-ray diffraction pattern as shown in the following table:
2θ（°） interplanar spacing (A) Relative intensity (I/I) 0 )×100 4.64 ±0.25 19.02 ±0.55 vw 6.69 ±0.25 13.20 ±0.45 vs 7.50 ±0.25 11.77 ±0.40 m-s 9.46 ±0.25 9.34 ±0.35 w 10.05 ±0.25 8.80 ±0.30 m-s 12.02 ±0.25 7.35 ±0.30 vw-w 13.44 ±0.25 6.58 ±0.25 w 14.20 ±0.25 6.23 ±0.25 vw-w 15.32 ±0.25 5.78 ±0.20 vw-w 17.04 ±0.25 5.20 ±0.20 vw 18.07 ±0.25 4.91 ±0.20 vw-w 19.02 ±0.25 4.66 ±0.15 w-m 20.15 ±0.25 4.40 ±0.15 w-m 21.55 ±0.25 4.12 ±0.15 w-m 23.35 ±0.25 3.77 ±0.10 vw-w 24.40 ±0.25 3.64 ±0.10 vw-w 26.99 ±0.25 3.30 ±0.10 w-m 27.85 ±0.25 3.20 ±0.05 vw-w 28.80 ±0.25 3.10 ±0.05 vw-w 30.27 ±0.25 2.95 ±0.05 vw-w
。
7. A process for preparing the ITQ-26 molecular sieve according to any one of claims 1 to 6, 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 ITQ-26 molecular sieve; wherein the organic template Q is selected from substances containing 1,3-bis (1-adamantyl) imidazolium ions.
8. The method of claim 7, wherein: the organic template agent Q is hydroxide containing 1,3-bis (1-adamantyl) imidazolium ions.
9. The method of claim 7, wherein: the structural formula of the 1,3-bis (1-adamantyl) imidazolium ion is as follows:
。
10. the method of claim 7, wherein: the heteroatom element X is at least one selected from aluminum, boron, gallium, titanium, zirconium, hafnium, tin, zinc, iron, indium and chromium.
11. The method of claim 7, wherein: the organic template agent Q and the silicon source are prepared from 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= 0.15~4: 1: 0.01~0.0.2-4:0.5-30:0-0.1:0.2-4; wherein the method comprises the steps ofmIn the oxidation state of the element X,m= 1~7。
12. the method of claim 11, wherein: the organic template agent Q and the silicon source are prepared from 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= 0.3~1.5: 1: 0.04~0.2: 0.005~0.05: 0.35~2.5: 5~15。
13. The method of claim 7, wherein: 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 germanium; the fluorine source is at least one selected from hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride.
14. The method of claim 13, wherein: the fluorine source is at least one selected from hydrofluoric acid and ammonium fluoride.
15. The method of claim 7, wherein: the crystallization conditions include: crystallizing at 100-200 ℃ for 72-720 hours.
16. A molecular sieve composition characterized by: comprising the ITQ-26 molecular sieve of any one of claims 1 to 6 or the ITQ-26 molecular sieve prepared according to the method of any one of claims 7 to 15, and a binder.
17. Use of the ITQ-26 molecular sieve of any one of claims 1 to 6 or the ITQ-26 molecular sieve prepared according to the process of any one of claims 7 to 15, or the ITQ-26 molecular sieve composition of claim 16, as an adsorbent or catalyst.
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