CN114538466B - Super macroporous silicate molecular sieve ZEO-1, its synthesis method and use - Google Patents

Super macroporous silicate molecular sieve ZEO-1, its synthesis method and use Download PDF

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CN114538466B
CN114538466B CN202011346698.4A CN202011346698A CN114538466B CN 114538466 B CN114538466 B CN 114538466B CN 202011346698 A CN202011346698 A CN 202011346698A CN 114538466 B CN114538466 B CN 114538466B
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molecular sieve
sio
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mineralizer
zeo
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CN114538466A (en
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陈飞剑
高子豪
黎建
林聪�
林清芳
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Anhui Zeou New Material Technology Co ltd
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Priority to EP21896762.8A priority patent/EP4253321A1/en
Priority to PCT/CN2021/129234 priority patent/WO2022111261A1/en
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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    • B01J29/00—Catalysts comprising molecular sieves
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    • 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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    • C01B39/04—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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    • C01B39/02—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
    • 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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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract

The invention relates to a silicate molecular sieve ZEO-1 with a novel structure, a synthesis method and application thereof, and features of X-ray powder diffraction, pore canal system and topology of the molecular sieve are characterized. Under alkaline conditions (with OH ‑ As mineralizer) or neutral conditions (in F ‑ As mineralizer) can synthesize the molecular sieve. The molecular sieve has good thermal stability and can be used as an adsorbent or a catalyst.

Description

Super macroporous silicate molecular sieve ZEO-1, its synthesis method and use
Technical Field
The invention relates to a silicate molecular sieve ZEO-1 with super macroporous structure, and also relates to a synthesis method and application thereof.
Background
Molecular sieve materials are a group of materials consisting of TO 4 (T represents an oxidation state atom with +4 or +3 in general, such as Si, P, al, B, ge, ga, etc., and T atom means a tetrahedral atom, namely a skeleton atom participating in the skeleton of the molecular sieve) tetrahedral forms a class of inorganic microporous solid materials through sharing vertexes. In general, the composition of a molecular sieve can be represented by the following empirical formula: x (M) 1/n AO 2 ):yYO 2 :zR:qH 2 O, wherein M represents one or more +n-valent organic or inorganic cations; a represents one or more trivalent elements; y represents one or moreA tetravalent element, typically Si; r represents one or more organic molecules. The chemical composition of a molecular sieve of a particular structure obtained by a particular synthesis process, whether it be the product of a fresh synthesis or a sample after calcination treatment, will generally have a particular interval of variation. In addition, a molecular sieve of a specific structure needs to be further distinguished by powder X-ray diffraction, because the different molecular sieves have different pore structures due to the different crystal structures, and completely different diffraction patterns are obtained in the test of powder X-ray diffraction. The most important characteristics of molecular sieves are their variable pore chemical composition, adjustable pore diameter and pore shape. These excellent properties have given molecular sieve materials broad applications in adsorption, separation, catalysis, microelectronics, medical diagnostics, and the like.
The uniqueness of molecular sieve materials of different structures is manifested in their unique X-ray powder diffraction pattern and different chemical composition. The position, relative intensity and width of the powder X-ray diffraction peaks are related to the chemical composition of the material, grain size and shape, etc., and the powder X-ray diffraction patterns of different samples may be slightly different due to the influence of the variation of the unit cell parameters. In addition, the uniqueness of molecular sieve materials of different structures can also manifest themselves in their unique topology. According to the definition and interpretation of the International molecular Screen Association, the coordination sequence (Coordination Sequences) and Vertex symbol (Vertex Symbols) are unique when taken together for a particular molecular Screen topology framework, i.e., they can be used to explicitly distinguish between different molecular Screen framework structures (see International molecular Screen Association's official networks https:// outline. IZA-structure. Org/IZA-SC/databaseHelp_structures. Html#CS).
Molecular sieve materials can be classified into small pore, medium pore, large pore and ultra large pore molecular sieves according to the number of rings of the pore canal, and the molecular sieve materials respectively have window ring numbers below 8-membered ring, below 10-membered ring, below 12-membered ring and above 12-membered ring. The pore size of the molecular sieve material successfully applied in industry is generally below 1nm, which greatly limits the molecular size and shape of the reaction substrate in the adsorption, separation and catalysis processes, and becomes a stopper in the practical application of the molecular sieve material. The development and acquisition of stable ultra-large pore molecular sieves, even mesoporous molecular sieves, with pore channels ranging from 1nm to 2nm in diameter has been a great challenge for inorganic chemists. This kind of material will open the door for new catalytic applications in the fields of petrochemistry, fine chemistry and life sciences.
Because of the stability of silicate materials, the super macroporous silicate molecular sieve material has important application prospect. However, it is known that crystallization of large and ultra large pore silicate molecular sieves is very difficult, and the number of silicate molecular sieve materials having an ultra large pore structure that have been synthesized is very limited, and so far, there are only less than 20 types of ultra large pore silicate molecular sieve materials having more than 16 membered rings (including 16 membered rings), for example, ITQ-37[ j.sun et al., nature,2009,458,1154-1157], ITQ-43[ j.jiang et al., science,2011,333,1131-1134] and ITQ-33[ a.corna et al., nature 2006,443,842-845], NUD-1[F.—j.chen et al., angel. Chem. Int. Ed.2014,53,9592-9596], and ECR-34[K.G.Strohmaier et.al, j.am. Chem. Soc.2003,125,16035-16039], etc., of which most of the materials are germanium-containing molecular sieves. It is well known that, besides being expensive, germanium-containing molecular sieves are extremely easy to absorb water to generate framework collapse after removing organic matters in pore channels, thus severely limiting the large-scale industrial application of the molecular sieves.
On the other hand, molecular sieves widely industrialized or having industrial catalytic applications are all molecular sieves of multi-dimensional pore channels, such as ZSM-5, Y-type molecular sieves, A-type molecular sieves, and the like. To date, of all the reported novel molecular sieves of known structure, all stable, pure or high silicon ultra-large pore molecular sieves do not have multi-dimensional ultra-large pore channels; all molecular sieves with multi-dimensional oversized pores, all containing germanium or aluminum phosphate molecular sieve materials, have limited their use due to their stability and expensive cost.
WO2013019462A1 discloses a synthetic superporous silicate molecular sieve EMM-23 and a process for its preparation. The method uses quaternary ammonium double cations to synthesize a pure silicon pore structure, and an opening pore of the pure silicon pore structure is an adjustable 21-24 membered ring. However, the material has a si—oh structure, which affects the usable volume of its channels and reduces the structural stability.
US5489424 discloses a super macroporous silicate molecular sieve UTD-1 and a method for preparing the same, wherein the organic template agent is a complex metal complex (pentamethyl cobaltocene cation). US6043179 discloses a superporous silicate molecular sieve CIT-5 and a method for preparing the same, wherein the organic template agent is a complex drug derivative (methylated staramine cation). Both materials have not been widely used in industry due to the following two drawbacks: (1) The two structures only have one-dimensional 14-membered ring pore canal, and do not have the requirement of multidimensional pore canal required by industrial catalysis; (2) The organic templates necessary for synthesizing these two materials are extremely expensive, increasing the cost of commercialization.
CN104370296A discloses a super macroporous silicate molecular sieve NUD-1 and a preparation method thereof. The structure of the molecular sieve is alternately connected through a double quaternary ring, a ternary ring and a double ternary ring, so that a pore channel structure with ten-membered rings and twelve-membered rings alternately existing is formed, and the two pore channels are respectively crossed with 18-membered ring channels. However, the molecular sieve is a germanium-containing molecular sieve.
Thus, there is a need for germanium-free, low cost, stable silicate molecular sieve materials having a multi-dimensional ultra-large pore structure.
Disclosure of Invention
In a first aspect, the present invention provides a totally new ultra-large pore silicate molecular sieve ZEO-1. The material is a germanium-free, high-silicon or pure-silicon super macroporous molecular sieve material, has very important practical application value, and has very important theoretical significance for enriching molecular sieve structure families.
The ultra-large pore silicate molecular sieve of the present invention has the powder X-ray diffraction characteristics shown in table 1:
TABLE 1
In the above data w, mw, m, s, vs represents diffraction peak intensities, w is weak, mw is moderately weak, m is medium, s is strong, vs is very strong, as will be appreciated by those skilled in the art. Generally, w is less than 10, mw is 10-20, m is 20-40, s is 4-70, vs is greater than 70.
In a second aspect, the present invention also provides a method for preparing the above ultra-large pore molecular sieve, the method comprising:
(1) Mixing a silicon source, a boron group element compound, an organic template agent, water and a mineralizer to obtain a mixture;
(2) Crystallizing the mixture;
(3) Roasting the crystallized product to remove the template agent,
wherein the organic template agent has a tetrahedral space configuration represented by the following general formula:
wherein R is 1 Is cyclohexyl; r is R 2 、R 3 Is phenyl or cyclohexyl; r is R 4 Is C 1-8 Alkyl, preferably C 1-4 Alkyl, more preferably C 1-2 An alkyl group; x is phosphorus or nitrogen, preferably phosphorus.
The super macroporous silicate molecular sieve not only adds a new member for the super macroporous molecular sieve material family, but also provides a new choice for the application of the super macroporous molecular sieve material in industrial catalysis.
In a third aspect, the present invention also provides a molecular sieve composition comprising the ultra-large pore silicate molecular sieve of the present invention and a binder.
In a fourth aspect, the molecular sieve composition of the present invention may be used as an adsorbent or catalyst.
Drawings
FIG. 1 is a powder X-ray diffraction pattern (light source is Cu target K alpha rays) of the molecular sieve of the invention before and after the template agent is removed by high-temperature calcination at 600 ℃ and 1000 ℃.
FIG. 2 is an X-ray diffraction pattern (light source is synchrotron radiation, wavelength 0.457926A) of the synthesized molecular sieve of the invention.
FIG. 3 is a Scanning Electron Microscope (SEM) of the molecular sieve of the present invention.
Fig. 4 is a diagram of the structure of the channels of the molecular sieve of the present invention.
Detailed Description
The crystal structure of the ZEO-1 molecular sieve of the present invention is shown in FIG. 4. As can be seen from FIG. 4, there are through 16-and 12-membered ring channels in both the a-axis and b-axis directions of the ZEO-1 crystal structure. In addition, 16 and 12 membered ring channels exist in the direction of the near (a+b+c) axis of the ZEO-1 crystal structure. Thus, the structure is described as a three-dimensional cross-channel system of (16+12) x (16+12) membered rings.
The ZEO-1 molecular sieve of the present invention has, through structural analysis and topology analysis, a molecular sieve framework structure having 21 topologically independent T atoms, 43 topologically distinct ribs (lines of adjacent T atoms and T atoms), 41 topologically distinct faces (planes of T atoms), and 19 topologically distinct building blocks of T atoms. Wherein the skeleton structure of the ZEO-1 material has the topological properties (including coordination sequence and vertex symbol) of 21 topologically independent T atoms, and the topological characteristics thereof are shown in table 2:
TABLE 2
From T1 to T21, 21 topologically different T atoms representing the framework structure ZEO-1 of the ultra-large pore molecular sieve of the invention; from N1 to N12, the coordination sequence of these T atoms from the first layer to the twelfth layer is represented. Because of the different order of T atom naming, 21 topologically independent T atoms named in different orders may not be in one-to-one correspondence with the coordination sequence and vertex symbol of the T atom order of the table, but the structures belonging to the ZEO-1 topology all include and only include the coordination sequence and vertex symbol of the 21 topologically independent T atoms in the table, and the coordination sequence and vertex symbol are in one-to-one correspondence.
Among the 19 diverse building blocks in the framework structure of the ZEO-1 material, there are three supercage structures: the first super-cage structure has openings for 4 16-membered rings, the second super-cage structure has openings for 2 16-membered rings and 2 12-membered rings, and the third super-cage structure has openings for 4 12-membered rings. Compared to the 4-12-membered ring-opening supercage structure of Y-type zeolite (structure code: FAU), which is also an important catalytic center for Y-type zeolite, ZEO-1 has larger pore channels, more available volume and more abundant pore channel diversity.
The ZEO-1 molecular sieve of the invention has a chemical composition of (HAO) 2 ) x ·SiO 2 Wherein A represents a boron group element, preferably Al or B, more preferably Al; x=0 to 1.0, preferably x=0 to 0.5, more preferably x=0 to 0.2.
After calcination for 3 hours at 1000 ℃ in an air atmosphere to remove the template molecules, the ZEO-1 molecular sieve of the present invention remains framework stable (as shown in fig. 2), showing better stability compared to the ultra-large pore molecular sieve materials of the prior art. Meanwhile, hetero atoms such as aluminum, boron and the like can be directly doped into the molecular sieve framework. These characteristics endow the molecular sieve material with potential application prospects in the fields of adsorption, separation, catalysis and the like.
Specific examples of organic template agents in the synthesis method of the ultra-large pore molecular sieve of the present invention include, but are not limited to, any one or more of those shown in table 3:
TABLE 3 Table 3
The organic template is preferably selected from any one or more of template 1, template 6, template 7 and template 8, more preferably selected from any one or more of template 6 and template 8.
The synthetic method of the ultra-large pore molecular sieve comprises the following steps:
(1) Under static or dynamic stirring, uniformly mixing a silicon source, a boron group element compound, an organic template agent, water and a mineralizer according to a proportion, wherein the obtained mixture forms a reaction gel, and the chemical composition of the reaction gel is rOH: aHF: xA 2 O 3 :SiO 2 :wH 2 O, wherein R represents a positively charged group of the organic template; a represents Al or B; the corresponding values of r, a, x and w are respectively as follows: r=0.1-5.0, a=0-5.0, x=0-1.0, w=1-100;
(2) Placing the reaction gel under an infrared lamp or in an oven, removing redundant solvent, transferring the reaction gel into a stainless steel reaction kettle, and reacting for 1-60 days, preferably 2-45 days at 80-240 ℃ and preferably 120-220 ℃ under a sealed condition for crystallization;
(3) Washing, centrifuging and drying the crystallized product, and roasting for 2-5 hours in an air atmosphere at 400-650 ℃ to remove the template agent.
In step (1), the chemical composition rrrOH: aHF: xA of the reaction gel 2 O 3 :SiO 2 :wH 2 In O, A is preferably Al or B; the values of r, a, x and w are preferably respectively as follows: r=0.1-2.0, a=0-2.0, x=0-0.5, w=1-30.
The silicon source may be at least one selected from silicic acid, silica gel, silica sol, tetraalkyl silicate and water glass, preferably water glass, silica sol or tetraethyl orthosilicate. The boron group element compound may be at least one selected from sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecanoate, aluminum hydroxide or boric acid, and is preferably sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecanoate or boric acid. The mineralizer may be OH derived from an alkaline organic template solution - Or from additionally added HF or NH 4 F of F - . The addition of mineralizers may accelerate crystallization of the molecular sieve and may be beneficial for structure targeting. The preparation method of the invention is carried out under neutral conditions (F - Mineralizer) and alkaline conditions (no HF, with OH - As mineralizer) can all give the molecular sieve ZEO-1 according to the invention.
In the preparation method of the present invention, germanium or a germanium-containing compound is not used.
The materials may be added and mixed in any order. For example, boron group element (Al or B) may be added to the resulting alkaline template solution, dissolved with stirring, and then a suitable silicon source may be added. If necessary, adding mineralizer after stirring uniformly, heating under an infrared lamp or in an oven to remove excessive solvent in the system, and obtaining the target gel.
Before preparing the reaction gel, all the organic cation template agent can be exchanged into hydroxide form through ion exchange resin, the concentration of the organic cation template agent is calibrated through 0.1M hydrochloric acid solution for later use, and the organic cation template agent can also be directly introduced in the form of chloride, bromide or iodide.
In step (2), the temperature of the oven may be, for example, 80 ℃.
The crystallization conditions may include, for example: the crystallization temperature is 80 to 240 ℃, preferably 120 to 220 ℃, more preferably 140 to 210 ℃; the crystallization time is 1 to 60 days, preferably 2 to 45 days, more preferably 3 to 30 days.
The mixture of the preparation method of the invention may further comprise seed crystals. The seed crystal may be contained in an amount of 0.01ppm by weight to 10000ppm by weight. The ultra large pore molecular sieve of the present invention may be used as seed crystals. The existence of the seed crystal can accelerate the reaction process and reduce the reaction cost.
In step (3), washing, centrifuging and drying may be performed in any manner conventionally known in the art. For example, the washing may be performed with water or ethanol for a plurality of times; drying can be performed by adopting a drying mode.
Examples
In order to more clearly illustrate the present invention, the following examples are set forth. These examples do not limit the scope of the invention in any way.
Example 1
The general synthesis of the template will be described with template 6 as an example. 28.04g of tricyclohexylphosphine and 150ml of acetonitrile were mixed in a 250ml round bottom flask. 21.29g of methyl iodide was dropwise added to the mixture at ordinary temperature. The system is reacted for two days at normal temperature under the stirring state, the solvent of the reaction mixture is removed by rotary evaporation to obtain a crude product, and 40.55g of the product is obtained by ethanol recrystallization, and the yield is 96%. The product was subjected to liquid nuclear magnetism (D 2 O) and electrospray mass spectrometry characterization, confirmed as the target compound.
The resulting product was dispersed in 400ml of deionized water, and column-exchanged by a pretreated 717 strong base anion exchange resin (manufacturer: national drug group), to exchange the resulting aqueous solution of template 6. An appropriate amount of this solution was weighed, calibrated with 0.1mol/L hydrochloric acid solution, and phenolphthalein as an indicator. The calibrated structure demonstrates that the exchange efficiency of iodized salt to hydroxyl reaches 97%.
Example 2
In a molar ratio of 0.5ROH to 0.5HF to 0.01Al 2 O 3 :SiO 2 :5H 2 The O ratio prepares a molecular sieve synthesized gel, generally as follows: an appropriate amount of the exchanged template solution of example 1 was weighed, 0.04mmol (0.008 g) of aluminum isopropoxide powder was added thereto, stirred for about half an hour to allow 2mmol (0.417 g) of tetraethyl orthosilicate to be added thereto, stirred at normal temperature for about two hours to allow the tetraethyl orthosilicate to be completely dissolved, then a corresponding amount of hydrofluoric acid solution was added thereto in the above-mentioned ratio, stirred uniformly, and the mixed gel was placed under an infrared lamp or in an oven at 80 ℃ to remove the excess solvent. Transferring the finally obtained reaction gel into a 5ml stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 28 days at 175 ℃ under a sealed condition, washing the product twice by water and ethanol, and drying for later use. The product was used directly for X-ray powder diffraction phase identification and was identified as ZEO-1. Taking a proper amount of sample, calcining in a muffle furnace at 600 ℃ in air atmosphere for 2 hours to remove template agent, washing the product, centrifuging, drying, and performing elemental analysis to show that the silicon-aluminum ratio is 20.5, and the molecular formula is (HAlO) 2 ) 0.047 ·SiO 2 。
Example 3
In a molar ratio of 0.5ROH to 0.5HF to 0.02Al 2 O 3 :SiO 2 :7H 2 The O ratio prepares a molecular sieve synthesized gel, generally as follows: a proper amount of the exchanged template solution of example 1 was weighed, 0.08mmol (0.016 g) of aluminum isopropoxide powder was added thereto, stirred for about half an hour to allow 2mmol (0.417 g) of tetraethyl orthosilicate to be added thereto, stirred at room temperature for about two hours to allow the tetraethyl orthosilicate to be completely dissolved, then a corresponding amount of hydrofluoric acid solution was added thereto in the above-mentioned ratio, stirred uniformly, and the mixed gel was placed under an infrared lamp or in an oven at 80℃to remove the surplus solvent. Condensing the finally obtained reactionTransferring the gel into a 5ml stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 7 days at 190 ℃ under a sealed condition, washing the product twice by water, washing twice by ethanol, and drying for later use. The product was used directly for X-ray powder diffraction phase identification and was identified as ZEO-1. Taking a proper amount of sample, calcining in a muffle furnace at 600 ℃ in air atmosphere for 2 hours to remove template agent, washing the product, centrifuging, drying, and performing elemental analysis to show that the silicon-aluminum ratio is 14.6, and the molecular formula is (HAlO) 2 ) 0.064 ·SiO 2 。
Example 4
According to the molar ratio of 0.5ROH to 0.01Al 2 O 3 :SiO 2 :10H 2 The O ratio prepares a molecular sieve synthesized gel, generally as follows: a suitable amount of the exchanged template solution of example 1 was weighed, 0.04mmol (0.008 g) of aluminum isopropoxide powder was added thereto, stirred for about half an hour to add 2mmol (0.417 g) of tetraethyl orthosilicate, stirred for about two hours at normal temperature to completely dissolve the tetraethyl orthosilicate, and the mixed gel was placed under an infrared lamp or in an oven at 80℃to remove the excess solvent. Transferring the finally obtained reaction gel into a 15ml stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 30 days at 175 ℃ under a sealed condition, washing the product twice by water, washing twice by ethanol, and drying for later use. The product was used directly for X-ray powder diffraction phase identification and was identified as ZEO-1. Taking a proper amount of sample, calcining in a muffle furnace at 600 ℃ in air atmosphere for 2 hours to remove template agent, washing the product, centrifuging, drying, and performing elemental analysis to show that the silicon-aluminum ratio is 20.8, and the molecular formula is (HAlO) 2 ) 0.046 ·SiO 2 。
Example 5
According to the mol ratio of 0.5ROH to 0.0167Al 2 O 3 :SiO 2 :10H 2 The O ratio prepares a molecular sieve synthesized gel, generally as follows: a proper amount of the exchanged template solution of example 1 was weighed, 0.067mmol (0.013 g) of aluminum isopropoxide powder was added thereto, stirred for about half an hour to add 2mmol (0.417 g) of tetraethyl orthosilicate, stirred at room temperature for about two hours to completely dissolve the tetraethyl orthosilicate, and the mixed gel was placed under an infrared lamp or in an oven at 80℃to removeExcess solvent. Transferring the finally obtained reaction gel into a 15ml stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 15 days at 190 ℃ under a sealed condition, washing the product twice by water, washing twice by ethanol, and drying for later use. The product was used directly for X-ray powder diffraction phase identification and was identified as ZEO-1. Taking a proper amount of sample, calcining in a muffle furnace at 600 ℃ in air atmosphere for 2 hours to remove template agent, washing the product, centrifuging, drying, and performing elemental analysis to show that the silicon-aluminum ratio is 14.5, and the molecular formula is (HAlO) 2 ) 0.065 ·SiO 2 。
Examples 2-5 all obtained molecular sieve materials that remained well-structured after calcination (600 ℃ or 1000 ℃) indicating that their structure was stable. The molecular sieve raw powder sample and the X-ray powder diffraction schematic diagrams after high-temperature calcination are shown in fig. 1 and 2. A sample of ZEO-1 crystals of the appropriate size was selected and a scanning electron micrograph was taken as shown in FIG. 3.
Example 6
The molecular sieves of examples 2-5 were subjected to a continuous rotation electron diffraction test (cRED) and the structural analysis results showed that the structure of the ZEO-1 molecular sieve had tetragonal symmetry, which was I4 1 The unit cell parameters obtained by synchrotron radiation diffraction (FIG. 2) refinement of the amp space group at a wavelength of 0.457926 angstrom are:
topology analysis was performed using the crystallographic structure file (CIF file) obtained after the cRED test. Topology analysis software was based on ToposPro 5.3.0.2 and analysis procedures and methods were based on the operating manual given on the official website of the software (see ToposPro official network: https:// topospro.com/software /).
Analysis results show that the molecular sieve framework structure has 21 topologically independent T atoms, 43 topologically different ribs, 41 topologically different faces, and 19 topologically different building blocks composed of T atoms. The more specific topological characteristics of the framework structure of the ZEO-1 molecular sieve are shown in table 2.

Claims (27)

1. A silicate molecular sieve is characterized in that the molecular sieve has X-ray powder diffraction characteristics shown in the following table,
and the crystal structure of the molecular sieve is provided with a three-dimensional cross pore canal system of (16+12) x (16+12) membered rings.
2. The molecular sieve of claim 1, wherein the framework of the molecular sieve has the topological characteristics shown in the following table.
3. Molecular sieve according to any of claims 1-2, characterized in that the molecular sieve has a chemical composition of (HAO 2 ) x ·SiO 2 Wherein a is Al or B, x=0-1.0.
4. A molecular sieve according to claim 3, characterized in that (HAO 2 ) x ·SiO 2 X=0-0.5.
5. A molecular sieve according to claim 3, characterized in that (HAO 2 ) x ·SiO 2 X=0-0.2.
6. The method for synthesizing a molecular sieve according to any one of claims 1 to 5, comprising:
(1) Mixing a silicon source, a boron group element compound, an organic template agent, water and a mineralizer to obtain a mixture;
(2) Crystallizing the mixture;
(3) Roasting the crystallized product to remove the template agent,
wherein the organic template is selected from any one or more of the following:
7. the method of claim 6, wherein the organic templating agent is selected from any one or more of the following:
8. the method of claim 6, wherein the organic templating agent is selected from any one or more of the following:
9. a method according to any one of claims 6-8, characterized in that the method comprises:
(1) Uniformly mixing a silicon source, a boron group element compound, an organic template agent, water and a mineralizer according to a proportion under stirring to obtain a mixture, wherein the obtained mixture forms a reaction gel, and the chemical composition of the reaction gel is rOH, aHF, xA 2 O 3 :SiO 2 :wH 2 O, wherein R represents a positively charged group of the organic template; a represents boron group element; the corresponding values of r, a, x and w are respectively as follows: r=0.1-5.0, a=0-5.0, x=0-1.0, w=1-100;
(2) Placing the reaction gel under an infrared lamp or in an oven, removing redundant solvent, transferring the reaction gel into a stainless steel reaction kettle, reacting for 1-60 days at 80-240 ℃ under a sealed condition, and crystallizing;
(3) Washing and drying the crystallized product, and roasting for 2-5 hours in an air atmosphere at 400-650 ℃ to remove the template agent.
10. The process according to claim 9, characterized in that the crystallization temperature in step (2) is 120-220 ℃.
11. The process according to claim 9, wherein the crystallization time in step (2) is 2 to 45 days.
12. The method according to claim 9, wherein rrOH is aHF is xA, the chemical composition of the reaction gel 2 O 3 :SiO 2 :wH 2 In O, A is Al or B.
13. The method according to claim 12, wherein rOH: aHF: xA 2 O 3 :SiO 2 :wH 2 In O, the corresponding values of r, a, x and w are respectively as follows: r=0.1-2.0, a=0-2.0, x=0-0.5, w=1-30.
14. The method according to any one of claims 6-8, characterized in that the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraalkyl silicate and water glass.
15. The method according to any one of claims 6 to 8, characterized in that the boron group element compound is selected from at least one of sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecanoate, aluminum hydroxide or boric acid.
16. The method according to any one of claims 6 to 8, characterized in that the mineralizer is OH derived from an aqueous alkaline organic template - 。
17. The method according to any one of claims 6 to 8, characterized in that the mineralizer is derived from additionally added HF or NH 4 F of F - 。
18. The method according to any one of claims 6 to 8, characterized in that the crystallization conditions in step (2) comprise: the crystallization temperature is 80 to 240 ℃; the crystallization time is 1 to 60 days.
19. The process according to claim 18, characterized in that the crystallization temperature in step (2) is 120 to 220 ℃.
20. The process according to claim 18, characterized in that the crystallization temperature in step (2) is 140 to 210 ℃.
21. The process according to claim 18, characterized in that the crystallization time in step (2) is 2 to 45 days.
22. The process according to claim 18, characterized in that the crystallization time in step (2) is 3 to 30 days.
23. The method according to any one of claims 6-8, characterized in that the mixture further comprises seed crystals.
24. The method of claim 23, wherein the mixture comprises 0.01ppm to 10000ppm by weight of seed crystals.
25. The method of claim 23, wherein the seed crystals comprise the molecular sieve of any one of claims 1-5.
26. A molecular sieve composition comprising the molecular sieve of any one of claims 1-5 or synthesized according to the method of any one of claims 6-25, and a binder.
27. Use of the molecular sieve composition of claim 26 as an adsorbent or catalyst.
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