CN110526256B - ECNU-n molecular sieve with cfi laminated plate structure and preparation method and application thereof - Google Patents
ECNU-n molecular sieve with cfi laminated plate structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an ECNU-n molecular sieve with a cfi laminated plate structure, a preparation method and application thereof, and the ECNU-n molecular sieve is characterized in that the molecular sieve is a 'first oxide, a second oxide and a third oxide' which form three cfi laminated plate structures connected between different layers. Compared with the prior art, the invention has an original structure, is discovered for the first time, can enrich the types of molecular sieves, and provides possibility for developing a novel environment-friendly catalytic system by introducing catalytic centers such as Al, ti, sn and the like into the framework of the molecular sieve to construct a solid acid or a redox catalyst based on a novel pore channel structure of the molecular sieve.
Description
Technical Field
The invention relates to the technical field of molecular sieves, in particular to a newly discovered ECNU-n (n =26,23, 22) series molecular sieve with a cfi layer plate structure and a preparation method and application thereof.
Background
The molecular sieve is TO4The inorganic porous material with a unique crystal structure and microporous channels constructed by (T = Si, al, ge, ti, sn, B and the like) tetrahedrons is widely applied to the fields of adsorption separation, ion exchange, catalysis and the like. The molecular sieve has wide application and benefits from the special chemical composition and unique structure, so the synthesis of the molecular sieve with new structure and new chemical composition has very important significance for expanding the application range of the molecular sieve. In general, most molecular sieves are hydrothermally synthesized by the action of a templating agentSmall portions can be synthesized without a template. The energy-density correlation results in a reversible crystallization process that tends to be lower in energy arrangement, so that the traditional hydrothermal synthesis method can limit the diversity of molecular sieve structures. In order to overcome the limitations of the conventional hydrothermal synthesis methods, researchers have developed various methods to synthesize novel molecular sieves, which mainly include developing organic templates with novel structures, introducing heteroatoms, post-treatment modification of structures, and the like. Based on the structural instability of the silicon germanium molecular sieve, the top-down strategy is adopted to controllably modify the structure of the existing silicon germanium molecular sieve, so that a series of molecular sieve materials with novel structures are created, and the molecular sieve materials are one of the hot points of research in the field of molecular sieves.
Disclosure of Invention
The invention aims to provide an ECNU-n molecular sieve with a cfi laminated plate structure and a preparation method and application thereof, wherein three novel molecular sieves with the same cfi laminated plate and different interlayer connection structures are prepared by adopting a method of controllably hydrolyzing interlayer double four-membered rings at room temperature, the three molecular sieves are confirmed to have original structures and novel pore channels by XRD spectrograms, and materials with corresponding frameworks containing catalytic centers such as Al, ti, sn and the like provide possibility for developing a novel environment-friendly catalytic system and can enrich the types of the molecular sieves for the first time.
The specific technical scheme for realizing the purpose of the invention is as follows: an ECNU-n molecular sieve with a cfi laminated plate structure is characterized in that the molecular sieve has a chemical composition shown by a formula of 'first oxide/second oxide' or 'first oxide/second oxide/third oxide', and has three different interlayer connection cfi laminated plate structures represented by X-ray diffraction shown in the following tables 1,2 and 3:
table 1: structural data table of X-ray diffraction of ECNU-26 molecular sieves
Wherein: (a) is ± 0.30 °;
table 2: structural data table of X-ray diffraction of ECNU-23 molecular sieves
Wherein: (a) is ± 0.30 °;
table 3: structural data table of X-ray diffraction of ECNU-22 molecular sieves
Wherein: (a) is ± 0.30 °;
the first type of oxide is silicon oxide; the second oxide is germanium oxide; the third oxide is one or the mixture of more than two of aluminum oxide, boron oxide, ferric oxide, gallium oxide, titanium oxide, tin oxide, gallium oxide, rare earth oxide, indium oxide and vanadium oxide; the molar ratio of the first oxide to the second oxide to the third oxide is 1:0.1 to 0.6:0 to 0.05.
A preparation method of ECNU-n molecular sieve with a cfi laminated plate structure is characterized in that the ECNU-n molecular sieve is prepared according to the following steps:
preparation of (one) CTH silicon germanium molecular sieve parent body
Mixing a first oxide source (calculated as first oxide) with a second oxide source (calculated as second oxide), a third oxide source, an organic template, and a fluorine source (calculated as F)-Calculated) and water are added according to the ratio of 1:0.1 to 0.6:0 to 0.05:0.2 to 1.0: 0.2-0.75: 5 to 30 mol ratio, aging for 1 to 10 hours at the temperature of between 35 and 80 ℃, crystallizing for 14 to 40 days at the temperature of between 150 and 180 ℃, filtering, washing and drying the crystallized product, and then heating to 500 to 800 DEG CRoasting for 5-8 hours to prepare a silicon germanium molecular sieve matrix with a CTH topological structure; the fluorine source is one or a mixture of more than two of hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride; the organic template agent is an imidazole compound with the following structural formula:
wherein: r is1、R2And R3Being alkyl radicals C of different carbon chain numbers1～6Preferably alkyl C1～3(ii) a The counter anion of the quaternary nitrogen structure may be a halogen ion or a hydroxide ion OH —, but is not limited thereto.
Preparation of ECNU-n molecular sieve
Placing the silicon-germanium molecular sieve with the CTH topological structure in aqueous solution with the pH value of 1-13, magnetically stirring for 1-36 hours at room temperature, and roasting a product at the temperature of 500-800 ℃ for 5-8 hours after carrying out suction filtration, washing and drying to obtain the ECNU-n molecular sieve with the n =26,23,22 series structure;
the pH value of the aqueous solution is adjusted to 11-13 by adopting inorganic or organic alkali.
The ECNU-n molecular sieve is in a powdery, granular or membrane product state in a roasting state.
The application of the ECNU-n molecular sieve with the cfi laminated plate structure is characterized in that the ECNU-n molecular sieve is used as a catalyst for catalytic reactions of olefin epoxidation, disproportionation/isomerization of m-alkyl substituted aromatic hydrocarbon and oxidation of ketone Baeyer-Villiger, wherein the molar ratio of the ECNU-n molecular sieve to olefin in the olefin epoxidation reaction is 0.03-0.3; the molar ratio of the ECNU-n molecular sieve to the alkyl substituted aromatic hydrocarbon in the disproportionation/isomerization reaction of the m-alkyl substituted aromatic hydrocarbon is 0.1-1; the molar ratio of ECNU-n molecular sieve to ketone in the ketone Baeyer-Villiger oxidation reaction is 0.1-1.
Compared with the prior art, the invention has an original structure, is discovered for the first time, can enrich the types of molecular sieves, and provides possibility for developing a novel environment-friendly catalytic system by introducing Al, ti, sn and other catalytic centers into the framework of the molecular sieve to construct a solid acid catalyst or a redox catalyst based on a novel pore channel structure of the molecular sieve.
Drawings
FIG. 1 is an X-ray diffraction pattern of ECNU-26 prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of Ti-ECNU-26 prepared in example 2;
FIG. 3 is an X-ray diffraction pattern of Al-ECNU-23 prepared in example 3;
FIG. 4 is an X-ray diffraction pattern of Sn-ECNU-22 prepared in example 4.
Detailed Description
The invention takes a CTH molecular sieve as a matrix, which has two mutually perpendicular fourteen-membered ring channels along the c direction and ten-membered ring channels along the b direction, and hydrolyzes the molecular sieve at room temperature to prepare the novel molecular sieve, and the preparation of the invention is further detailed by specific examples.
Example 1
1.31g of germanium oxide was put into an aqueous solution of 21.81g of 25% by mass of 1, 2-dimethyl-3- (3-methylbenzene) imidazolium hydroxide template and stirred until the solution was clear, 10.42g of tetraethyl orthosilicate and 0.96g of hydrofluoric acid (40% by mass) were added to the solution, and excess water was removed by a water bath at a temperature of 60 ℃ so that the molar ratio of the final water of the synthesized gel to silicon oxide was 10. The gel product was transferred to a stainless steel autoclave with a teflon liner for crystallization at 160 ℃ for 20 days. And (3) filtering, washing and drying the crystallized product, and roasting at 600 ℃ for 6 hours to obtain the CTH molecular sieve matrix. Placing the mixture into an ammonia water solution with the mass fraction of 0.4wt% and stirring vigorously for 12 hours, filtering, washing and drying the mixture, and roasting the mixture for 6 hours at the temperature of 580 ℃ to obtain 5.69 g of a product which is an ECNU-26 molecular sieve.
Referring to fig. 1, the ECNU-26 molecular sieve prepared above is characterized by a high resolution X-ray diffraction (XRD) pattern, and has the structural data of X-ray diffraction as shown in table 1 below:
table 1: structural data table of X-ray diffraction of ECNU-26 molecular sieves
(a)：±0.30°。
The above structural data indicate that the material has good crystallinity, and the inset is a model of the molecular sieve structure, which is believed to be that 50% of the double four-membered rings in the parent CTH framework are hydrolyzed to single four-membered rings, and the other 50% of the double four-membered rings remain unchanged, thus presenting channels in the direction c as fourteen and twelve membered rings, and in the direction b as ten and eight membered rings. In particular, the actual structure between ECNU-26 plates does not strictly alternate in the form of a double four-membered ring-a single four-membered ring-a double four-membered ring-a single four-membered ring.
Example 2
1.31g of germanium oxide was put into an aqueous solution of 17.45g of 25% by mass 1, 2-dimethyl-3- (3-methylbenzene) imidazolium hydroxide template and stirred until it was clear, and then 10.42g of tetraethyl orthosilicate, 0.86g of n-butyl titanate and 0.96g of hydrofluoric acid (40% by mass) were added to the above solution and excess water was removed in a water bath at 60 ℃ to obtain a final gel having a molar ratio of water to silicon oxide of 12. Transferring the gel product into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining for crystallization at 160 ℃ for 18 days, filtering, washing and drying the crystallized product, and roasting at 800 ℃ for 5 hours to obtain the CTH molecular sieve parent body with the titanium-containing framework. Placing the mixture into an ammonia water solution with the mass fraction of 0.6wt% and stirring vigorously for 12 hours, filtering, washing and drying the mixture, and roasting the mixture for 6 hours at the temperature of 600 ℃ to obtain 5.45 g of a product which is a Ti-ECNU-26 molecular sieve.
Referring to fig. 2, the Ti-ECNU-26 molecular sieve prepared above was characterized by a high resolution X-ray diffraction (XRD) pattern having the X-ray diffraction structural data shown in table 2 below:
table 2: structural data table of X-ray diffraction of Ti-ECNU-26 molecular sieves
(a)：±0.30°。
The above structural data indicate that the material has good crystallinity, and the inset is a molecular sieve structural model, the structure of which is considered that 50% of the double four-membered rings in the parent body CTH framework are hydrolyzed into single four-membered rings, and the other 50% of the double four-membered rings are kept unchanged, so that the material is presented as fourteen-membered ring and twelve-membered ring channels along the c direction, and ten-membered ring and eight-membered ring channels along the b direction. It is specifically noted that the actual structure between the ECNU-26 plates does not strictly alternate in the form of a double four-membered ring-a single four-membered ring-a double four-membered ring-a single four-membered ring.
Example 3
1.57g of germanium oxide was put into 26.17g of an aqueous solution of 25% by mass of 1, 2-dimethyl-3- (3-methylbenzene) imidazolium hydroxide as a template, stirred until it was clear, and then 10.42g of tetraethyl orthosilicate, 0.21g of sodium metaaluminate and 1.20g of hydrofluoric acid (40% by mass) were added to the solution, and excess water was removed in a water bath at 60 ℃ to give a final water-silica molar ratio of 10. Transferring the gel product to a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, crystallizing for 25 days at 160 ℃, filtering, washing and drying the crystallized product, roasting for 6 hours at 600 ℃ to prepare a CTH molecular sieve matrix with a framework containing aluminum, placing the CTH molecular sieve matrix into an ammonia water solution with the mass fraction of 8wt%, violently stirring for 10 hours, filtering, washing and drying, and roasting for 5.5 hours at 700 ℃ to obtain 5.82 g of the product Al-ECNU-23 molecular sieve.
Referring to fig. 3, the Al-ECNU-23 molecular sieve prepared above was characterized by a high resolution X-ray diffraction (XRD) pattern having the X-ray diffraction structural data shown in table 3 below:
table 3: structural data table of X-ray diffraction of Al-ECNU-23 molecular sieve
(a)：±0.30°。
The above structural data indicate that the material has good crystallinity, and the inset is a model of the molecular sieve structure, which is believed to be the product of the hydrolysis of all the two-four rings in the parent CIT-13 framework into a single four-membered ring, with two mutually perpendicular twelve-membered ring channels along the c-direction and eight-membered ring channels along the b-direction, respectively.
Example 4
2.10g of germanium oxide was put into an aqueous solution of 15.27g of 25% by mass of 1, 2-dimethyl-3- (3-methylbenzene) imidazolium hydroxide template and stirred until the solution was clear, 10.42g of tetraethyl orthosilicate, 0.88g of tin tetrachloride pentahydrate and 1.44g of hydrofluoric acid (40% by mass) were added to the solution, and excess water was removed in a water bath at a temperature of 60 ℃ to give a final water/silicon oxide molar ratio of 15. Transferring the gel product into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining for crystallization for 30 days at 160 ℃, filtering, washing and drying the crystallized product, roasting the crystallized product for 6 hours at 700 ℃ to prepare a matrix of the CTH molecular sieve with the framework containing tin, placing the matrix into an ammonia water solution with the mass fraction of 12wt%, violently stirring the matrix for 11 hours, filtering, washing and drying the matrix, and roasting the matrix for 7 hours at 600 ℃ to obtain 6.28 g of the product Sn-ECNU-22 molecular sieve.
Referring to FIG. 4, the Sn-ECNU-22 molecular sieve prepared above is characterized by a high resolution X-ray diffraction (XRD) pattern having the following X-ray diffraction pattern data as shown in Table 4:
table 4: structural data table of X-ray diffraction of Sn-ECNU-22 molecular sieve
(a)：±0.30°。
The above structural data indicate that the material has good crystallinity, and the inset is a model of the molecular sieve structure, which structure is believed to be that 50% of the double four-membered rings in the parent CTH framework are hydrolyzed to single four-membered rings, and the other 50% of the double four-membered rings are completely removed, where 50% is still a statistical result, so ECNU-22 exhibits twelve and ten membered ring channels in the c-direction and eight and six membered ring channels in the b-direction.
Example 5
The Ti-ECNU-26 catalyst prepared in example 1 above was characterized by its performance as a catalyst for olefin epoxidation under the following reaction conditions:
adding 50mg of Ti-ECNU-26 catalyst, 10mL of acetonitrile, 10mmol of n-hexene and 10mmol of hydrogen peroxide in turn into a round-bottom flask, stirring vigorously and refluxing for 2 hours in a water bath at the temperature of 60 ℃. After the reaction system is fully cooled, 0.1g of internal standard isopropanol is added, and the conversion rate of a substrate and the selectivity of a product are measured by using gas chromatography, wherein the conversion rate of n-hexene is 40%.
Example 6
The Al-ECNU-23 catalyst prepared in example 2 above was characterized by disproportionation/isomerization of meta-alkyl substituted aromatics under the following reaction conditions:
150mg of Al-ECNU-23 catalyst in a quartz tube with an inner diameter of 8nm in 30mL min-1N2Activated at 500 ℃ for 1 hour at a flow rate. After the activation is finished, the sample injection is started after the temperature is reduced to 350 ℃, and the feeding speed of the m-xylene is 0.5mL h-1The carrier gas is N2Flow rate of (2) 15mL min-1The mass space velocity (WHSV) under the condition is 4.34h-1. The cold trap is placed in an ice-water bath to collect the product, the quantitative analysis of the product is completed by gas chromatography,after 1 hour of reaction, the product, ortho-xylene, was in an amount comparable to that of para-xylene.
Example 7
The Sn-ECNU-22 catalyst prepared in example 3 above was characterized by the Baeyer-Villiger oxidation of ketones under the following reaction conditions:
100mg of Sn-ECNU-22 catalyst, 2mmol of 2-adamantanone, 10mL of solvent chlorobenzene and 4mmol of oxidant hydrogen peroxide are sequentially added into a round-bottom flask, and the mixture is refluxed in a water bath at the temperature of 75-90 ℃. After the reaction system is fully cooled, 0.1g of acetophenone is added, the conversion rate of a substrate and the selectivity of a product are measured by using gas chromatography, and after 6 hours of reaction, the conversion rate of the substrate of the product and the selectivity of lactone are close to 100 percent.
The above embodiments are only for further illustration of the present invention, and are not intended to limit the present invention, and all equivalent implementations of the present invention should be included within the scope of the claims of the present invention.
Claims (5)
1. Is provided withcfiECNU-nA molecular sieve is characterized in that the molecular sieve is composed of three oxides with different interlayer connection in a mode of ' first oxide/second oxide ' or ' first oxide/second oxidecfiECNU-nMolecular sieves of whichn=26, the first type of oxide is silica; the second type of oxide is germanium oxide; the third oxide is one or the mixture of more than two of aluminum oxide, boron oxide, ferric oxide, gallium oxide, titanium oxide, tin oxide, rare earth oxide, indium oxide and vanadium oxide; the molar ratio of the first oxide to the second oxide to the third oxide is 1:0.1 to 0.6:0 to 0.05; the structure data of the ECNU-26 molecular sieve by X-ray diffraction is shown in the following table 1:
table 1: structural data table of X-ray diffraction of ECNU-26 molecular sieves
Wherein: (a) is. + -. 0.30 ℃.
2. A composition as claimed in claim 1 havingcfiLaminated plate structure ECNU-nA process for the preparation of a molecular sieve,
characterized in that the ECNU-nThe molecular sieve is prepared by the following steps:
preparation of (I) CTH silicon germanium molecular sieve precursor
The first oxide, the second oxide, the third oxide, the organic template and the fluorine source are mixed with F-And water is counted according to the ratio of 1:0.1 to 0.6:0 to 0.05:0.2 to 1.0:0.2 to 0.75: 5-30 mol ratio, aging at 35-80 deg.C for 1-10 hours, crystallizing at 150-180 deg.C for 14-40 days, filtering, washing, drying, and calcining at 500-800 deg.C for 5-8 hours to obtain the final product; the first type of oxide is silicon oxide; the second oxide is germanium oxide; the third oxide is one or the mixture of more than two of aluminum oxide, boron oxide, iron oxide, gallium oxide, titanium oxide, tin oxide, rare earth oxide, indium oxide and vanadium oxide; the fluorine source is one or the mixture of more than two of hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride;
(II) ECNU-nPreparation of molecular sieves
Placing the silicon-germanium molecular sieve with the CTH topological structure in an aqueous solution with the pH value of 1-13, magnetically stirring for 1-36 hours at room temperature, and roasting a product for 5-8 hours at the temperature of 500-800 ℃ after carrying out suction filtration, washing and drying on the product to obtain the silicon-germanium molecular sieve with the CTH topological structurenECNU-nAnd (3) a molecular sieve.
3. The alloy of claim 2 havingcfiLaminated plate structure ECNU-nThe preparation method of the molecular sieve is characterized in that the pH value of the aqueous solution is adjusted to 11-13 by adopting inorganic or organic alkali.
4. The alloy of claim 2 havingcfiLaminated plate structure ECNU-nPreparation of molecular sievesPreparation method, characterized in that the ECNU-nThe molecular sieve is in a calcined state of powder, granule or membrane product.
5. A composition of claim 1 havingcfiECNU-nUse of molecular sieves characterized in that said ECNU-nMolecular sieve as catalyst for olefin epoxidation, disproportionation/isomerization of meta-alkyl substituted aromatics and catalytic reaction of ketone Baeyer-Villiger oxidation, wherein ECNU-nThe molar ratio of the molecular sieve to the olefin is 0.03 to 0.3; ECNU-nThe molar ratio of the molecular sieve to the alkyl substituted aromatic hydrocarbon is 0.1 to 1; ECNU-nThe molar ratio of the molecular sieve to the ketone is 0.1 to 1.
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| EP3162763A1 (en) * | 2015-10-30 | 2017-05-03 | Total Research & Technology Feluy SA | Simultaneous dehydration and skeletal isomerisation of isobutanol on ti-containing zeolite catalysts |
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