CN110357123B - High-crystallinity hierarchical-pore nano X-type molecular sieve and preparation method thereof - Google Patents

High-crystallinity hierarchical-pore nano X-type molecular sieve and preparation method thereof Download PDF

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CN110357123B
CN110357123B CN201910702128.5A CN201910702128A CN110357123B CN 110357123 B CN110357123 B CN 110357123B CN 201910702128 A CN201910702128 A CN 201910702128A CN 110357123 B CN110357123 B CN 110357123B
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邹继兆
刘丽佳
王洪宾
曾燮榕
吴洪亮
范金亚
余良
姚越超
涂文烜
刘莉
罗琪
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Shenzhen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Abstract

The invention relates to the technical field of synthesis of nano X-type molecular sieves, and particularly provides a high-crystallinity hierarchical porous nano X-type molecular sieve and a preparation method thereof. The preparation method comprises the steps of uniformly mixing N-methyl pyrrolidone, an alkali source, an aluminum source and water according to a certain proportion, then slowly adding a silicon source, uniformly stirring to form uniform sol, carrying out hydrothermal crystallization on the sol at 25-85 ℃ for 6-240 hours, washing a product to be neutral, drying and firing to obtain the high-crystallinity hierarchical pore nano X-type molecular sieve. The X-type molecular sieve is prepared by taking N-methylpyrrolidone as a structure directing agent, the particle size of the product is 20-200nm, the crystallinity is high, the dispersibility is good, the product has a hierarchical pore structure, and the X-type molecular sieve can be widely used as an adsorbent, an ion exchanger, a catalyst and a carrier or as a molecular sieve seed crystal.

Description

High-crystallinity hierarchical-pore nano X-type molecular sieve and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of nano X-type molecular sieves, and particularly relates to a high-crystallinity hierarchical porous nano X-type molecular sieve and a preparation method thereof.
Background
The X-type molecular sieve (FAU) is a rigid three-dimensional framework structure formed by connecting a silicon-oxygen tetrahedron and an aluminum-oxygen tetrahedron (the ratio of Si/Al of the framework is close to 1) through sharing oxygen atoms, the pore diameter of a micropore is about 0.7nm, the X-type molecular sieve has moderate acidity and good ion exchange capacity, has strong adsorption capacity on water, small molecular gas and the like, and is widely applied to the fields of petrochemical industry and the like. However, the traditional micron-sized molecular sieve has long microporous pore channels, is not beneficial to the rapid transmission of macromolecules, and easily causes the problem of diffusion limitation. The nano treatment of the molecular sieve can greatly improve the catalytic reaction activity and stability and improve the utilization rate of the zeolite. This is mainly due to the fact that the nano molecular sieve material has a large specific surface area, and can expose more active sites. Therefore, the design and construction of the function-oriented nano molecular sieve material are necessary. The preparation of the conventional nano X molecular sieve needs to use an organic template agent or a synthesis system involving high alkalinity, which increases the synthesis cost of materials on one hand and limits the framework silicon-aluminum ratio range of the obtained nano X molecular sieve on the other hand. For example, zhuangshan et al (cn200510016886.x) synthesizes LTA and FAU molecular sieve nano-scale crystals by using tetramethylammonium hydroxide (TMAOH) as a template, and the method has the disadvantages that expensive organic template agent TMAOH is used, the corrosivity is high, and a large amount of polluting toxic gas is generated when the template is removed by calcination. Reza Fazaeli et al synthesized a nano X zeolite molecular sieve (J.Phys.Theor.chem.IAU Iran,2011,8(3) 245-. Hussein Awala et al (Nature Materials,2015,14, 447) synthesizes monodisperse nano FAU zeolite under the condition of no organic template agent, the micropore crystallinity of the zeolite is low, aluminum powder is used as an aluminum source, and the aluminum powder generates a large amount of heat and hydrogen in the process of adding alkali liquor, and the feeding process is complex and slow, so that the large-scale industrial production is not facilitated.
Aiming at the problems and defects of the prior art, the invention provides a synthesis method for preparing a high-crystallinity hierarchical pore nano X-type molecular sieve by using a novel structure directing agent N-methylpyrrolidone, aiming at reducing the manufacturing cost and energy consumption of materials, providing a new method for synthesizing the hierarchical pore nano X-type molecular sieve and widening the synthesis and application of the nano molecular sieve.
Disclosure of Invention
The invention mainly aims to provide a high-crystallinity hierarchical porous nano X-type molecular sieve and a preparation method thereof, which can effectively solve the problems in the background technology.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-crystallinity hierarchical pore nano X-type molecular sieve comprises the following steps:
the method comprises the following steps: adding a certain amount of alkali source and aluminum source into deionized water, and stirring until the alkali source and the aluminum source are completely dissolved;
step two: adding a certain amount of N-methyl pyrrolidone into the solution obtained in the first step, and stirring and mixing uniformly to obtain a solution A;
step three: slowly adding a silicon source under the condition of strong stirring of the solution A, and continuously stirring to obtain sol B;
step four: transferring the sol B into a reaction container, and crystallizing for 6-240 hours at the temperature of 25-85 ℃;
step five: after the reaction is finished, carrying out solid-liquid separation, washing, drying and high-temperature calcination treatment on the solid product to obtain the high-crystallinity hierarchical porous nano X-type molecular sieve.
Preferably, the alkali source is an inorganic alkali source, and M is generated according to theory2Measuring the amount of O, and generating Al by an aluminum source according to a theory2O3Metering of the silicon source to theoretically form SiO2In the amount of N-methyl pyrrolidone NMP for short, and the mol ratio of each component in the sol B is M2O：Al2O3：SiO2：H2O: 1.0-15% of NMP: 1.0:1.8-15:40-450:0.6-13.8, M represents alkali metal.
Preferably, the alkali source is one or more of sodium hydroxide, sodium oxide and sodium carbonate;
the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, pseudo-boehmite, aluminum oxide, aluminum hydroxide, aluminum carbonate, aluminum powder, aluminum isopropoxide and aluminum acetate.
Preferably, the silicon source is one or more of water glass, white carbon black, sodium silicate, silica sol, ethyl orthosilicate, silica gel and diatomite.
Preferably, the stirring is performed intensively, and the rotation speed is 400-1500 rpm.
Preferably, the slow silicon source is added at a rate of 0.001mol/min to 5 mol/min.
Preferably, the reaction vessel is a sealed polytetrafluoroethylene reaction kettle or a glass flask.
Preferably, the heating device used under the condition of 25-85 ℃ is one or more of an oven, an oil bath, a water bath, a sand bath, an electric heating jacket and a microwave oven, and the crystallization condition is standing or stirring at 200-1000 r/min.
Preferably, the heating rate of the high-temperature calcination is 0.2-5 ℃ min-1Heating to 300-700 deg.C, calcining for 0.5-48 h.
And a highly-crystallized hierarchical pore nano X-type molecular sieve which has a mesoporous structure, has a particle size of (20-200) nm, and has a specific surface area of not less than 420m2g-1And the external surface area is not less than 50m2g-1(ii) a The silicon-aluminum ratio is 0.9-1.6.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method synthesizes the high-crystallinity multilevel nano X-type molecular sieve by taking the low-cost small molecular organic matter (N-methyl pyrrolidone) as the structure directing agent, the preparation method has simple and quick process, greatly reduces the synthesis process cost of materials, is expected to realize large-scale production and application, and the prepared high-crystallinity multilevel nano X-type molecular sieve has the characteristics of high crystallinity, small product particle size, large specific surface area and multilevel pore structure.
(2) The X-type molecular sieve prepared by the invention has the particle size of 20-200nm, small particle size, good monodispersity, high crystallinity, large specific surface area, hierarchical pore structure characteristic and potential application prospect in the fields of chemical industry, energy, electronics and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern (XRD) of the highly crystalline hierarchical porous nano X-type molecular sieve prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Micrograph (SEM) of the highly crystalline hierarchical porous nano X-type molecular sieve prepared in example 1 of the present invention;
FIG. 3 is a Transmission Electron Micrograph (TEM) of the highly crystalline hierarchical porous nano X-type molecular sieve prepared in example 1 of the present invention;
FIG. 4 shows N of the highly-crystallized hierarchical porous nano X-type molecular sieve prepared in example 1 of the present invention2Adsorption/desorption isotherm curves;
FIG. 5 is the BJH pore size distribution diagram of the high-crystallinity hierarchical-pore nano X-type molecular sieve prepared in example 1 of the present invention;
fig. 6 is an X-ray diffraction pattern (XRD) of the highly-crystallized multi-stage pore nano X-type molecular sieve prepared in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Adding 0.5g of sodium hydroxide and 1.2g of sodium aluminate into 6.7g of deionized water, and stirring until a clear solution is obtained;
(2) adding 3g N-methyl pyrrolidone (NMP) into the solution in the step (1);
(3) slowly dripping (0.005mol min) under the condition of quickly stirring the solution in the step (2) (the rotating speed is 500 r/min)-1According to SiO2Measured by mass) 3.88g of water glass (the content of the effective component is SiO)2 27.13wt％，Na2O8.74 wt%), and continuously stirring for 3 hours to obtain uniform sol;
(4) putting the sol obtained in the step (3) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at the constant temperature of 75 ℃ for 60 hours, wherein the molar ratio of each component in the reaction precursor is Na2O:Al2O3:SiO2:H2O:NMP＝1.43:1.0:2.4:70.2:4.1；
(5) After crystallization is finished, centrifuging and washing the solid product to be neutral, drying the solid product in a forced air oven at 50 ℃ for 24h, and calcining the solid product in air at the constant temperature of 400 ℃ for 5h (the heating rate is 1 ℃ for min)-1) And obtaining the nano X-type molecular sieve.
The sample prepared in example 1 (hereinafter referred to as Nano-X) was subjected to characterization analysis.
And (4) performing phase characterization on the Nano-X sample by using an X-ray diffractometer. The result is shown in figure 1, the XRD spectrum of the Nano-X sample is completely consistent with the characteristic peak of the standard X-type molecular sieve, and the synthetic Nano-X sample is the X-type molecular sieve.
The Nano-X sample was analyzed by X-ray fluorescence spectroscopy for a Si/Al ratio of 1.5.
And carrying out morphology characterization on the Nano-X sample by using a scanning electron microscope. As shown in FIG. 2, the morphology of the Nano-X sample is about 50-100nm in particle size and the particle size distribution is uniform, indicating that the synthesized sample is Nano-sized. The particle size of the synthesized Nano-X sample is further confirmed by a transmission electron microscope (fig. 3), and a large number of mesoporous pores exist among Nano-X nanoparticles, which is beneficial to the rapid transmission of catalytic macromolecular substances.
By using N2And (4) carrying out pore structure analysis on the Nano-X sample by using an adsorption and desorption analyzer. As shown in FIG. 4, N2The adsorption-desorption isotherm curves are represented by typical type IV adsorption isotherms, indicating that Nano-X has a hierarchical pore structure characteristic, which is consistent with TEM analysis results. The BET specific surface area is 704m2g-1External surface area of 89m2g-1. The pore diameter of the Nano-X is 0.56nm, the distribution diagram of the mesopores is shown in FIG. 5, the mesopore diameter is between 4.9 nm and 16nm, and the mesopore diameter is concentrated near 8.9 nm.
Example 2
(1) Adding 0.5g of sodium hydroxide and 1.2g of sodium aluminate into 6.7g of deionized water, and stirring until a clear solution is obtained;
(2) adding 4g N-methyl pyrrolidone (NMP) into the solution in the step (1);
(3) under the condition of strong stirring of the solution in the step (2)(the rotating speed is 500 r/min), slowly adding dropwise (0.005mol min)-1According to SiO2Measured by mass) 3.88g of water glass (the content of the effective component is SiO)2 27.13wt％，Na2O8.74 wt%), and continuously stirring for 3 hours to obtain uniform sol;
(4) putting the sol obtained in the step (3) into a hydrothermal reaction kettle, and crystallizing at the constant temperature of 75 ℃ for 60 hours, wherein the molar ratio of each component in the reaction precursor is Na2O:Al2O3:SiO2:H2O:NMP＝1.43:1.0:2.4:70.2:5.5；
(5) After crystallization is finished, centrifuging and washing the solid product to be neutral, drying the solid product in a forced air oven at 50 ℃ for 24h, and calcining the solid product in air at the constant temperature of 400 ℃ for 5h (the heating rate is 1 ℃ for min)-1) And obtaining the nano X-type molecular sieve.
The X-ray diffraction (XRD) of the sample is shown in figure 6, which shows that the synthesized sample is pure phase of X-type molecular sieve. The particle size is about 70 nm. The Si/Al ratio of the sample was 1.51 by X-ray fluorescence spectroscopy. N is a radical of2Adsorption/desorption isotherms and similar to FIG. 4, by calculating the BET specific surface area to be 588m2g-1External surface area of 116m2g-1。
Example 3
(1) Adding 0.5g of sodium hydroxide and 1.2g of sodium aluminate into 6.7g of deionized water, and stirring until a clear solution is obtained;
(2) slowly adding 2g N-methyl pyrrolidone (NMP) into the solution in the step (1);
(3) slowly dripping (0.007mol min) under the condition that the solution in the step (2) is intensively stirred (the rotating speed is 500 r/min)-1According to SiO2Calculated by weight) 3.88g of water glass (the content of the effective component is SiO)2 27.13wt％，Na2O8.74 wt%), and continuously stirring for 4 hours to obtain uniform sol, and standing for 24 hours;
(4) putting the sol obtained in the step (3) into a hydrothermal reaction kettle, and crystallizing at a constant temperature of 70 ℃ for 24 hours, wherein the molar ratio of each component in the reaction precursor is Na2O:Al2O3:SiO2:H2O:NMP＝1.43:1.0:2.4:70.2:2.8；
(5) After crystallization is finished, the solid product is centrifuged and washed to be inDrying in a 50 deg.C forced air oven for 24 hr, and calcining at 400 deg.C in air for 5 hr (heating rate of 1 deg.C for min)-1) And obtaining the nano X-type molecular sieve.
The X-ray diffraction pattern of the sample was substantially the same as that of FIG. 1, and the particle size was about 90 nm. The BET specific surface area is 597m2g-1External surface area of 50m2g-1。
Example 4
(1) Adding 2.67g of sodium hydroxide and 1.21g of sodium aluminate into 25g of deionized water, and stirring until a clear solution is obtained;
(2) adding 4g N-methyl pyrrolidone (NMP) into the solution in the step (1), and immediately placing the mixture into an ice bath;
(3) slowly adding 1.715g of white carbon black (0.008mol min) into the solution in the step (2) under the conditions of ice bath at 0 ℃ and rapid stirring (the rotating speed is 600 r/min)-1) Stirring in ice bath for 2h to obtain uniform sol, and standing for 24 h;
(4) putting the sol obtained in the step (3) into a hydrothermal reaction kettle, and crystallizing at the constant temperature of 60 ℃ for 48 hours, wherein the molar ratio of each component in the reaction precursor is Na2O:Al2O3:SiO2:H2O:NMP＝4.52:1.0:3.87:188:5.46；
(5) After crystallization is finished, centrifuging and washing the solid product to be neutral, drying the solid product in a forced air oven at 50 ℃ for 24h, and calcining the solid product in air at the constant temperature of 400 ℃ for 5h (the heating rate is 1 ℃ for min)-1) And obtaining the nano X-type molecular sieve.
The X-ray diffraction pattern of the sample is basically the same as that of figure 1, the particle size distribution is 100-200 nm, and the BET specific surface area is 497m2g-1External surface area of 116m2g-1。
Example 5
(1) Adding 2.67g of sodium hydroxide and 1.21g of sodium aluminate into 25g of deionized water, and stirring until a clear solution is obtained;
(2) adding 3g N-methyl pyrrolidone (NMP) into the solution in the step (1), and immediately placing the mixture into an ice bath;
(3) slowly adding 1.715g of white into the solution in the step (2) under the conditions of ice bath at 0 ℃ and rapid stirring (the rotating speed is 600 rpm)Carbon Black (0.005mol min)-1) Continuously stirring in an ice bath for 2 hours to obtain uniform sol, and standing for 24 hours;
(4) putting the sol obtained in the step (3) into a round-bottom flask with a condensing tube, and crystallizing at the constant temperature of 80 ℃ for 36h, wherein the molar ratio of each component in the reaction precursor is Na2O:Al2O3:SiO2:H2O:NMP＝4.52:1.0:3.87:188:5.46；
(5) After crystallization is finished, centrifuging and washing the solid product to be neutral, drying the solid product in a forced air oven at 50 ℃ for 24h, and calcining the solid product in air at the constant temperature of 400 ℃ for 5h (the heating rate is 1 ℃ for min)-1) And obtaining the nano X-type molecular sieve.
The X-ray diffraction pattern of the sample was substantially the same as that of FIG. 1, the particle size was about 100nm, and the BET specific surface area was 452m2g-1Outer surface area of 100m2g-1。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A preparation method of a high-crystallinity hierarchical pore nano X-type molecular sieve is characterized by comprising the following steps:
the method comprises the following steps: adding a certain amount of alkali source and aluminum source into deionized water, and stirring until the alkali source and the aluminum source are completely dissolved;
step two: adding a certain amount of N-methyl pyrrolidone into the solution obtained in the first step, and stirring and mixing uniformly to obtain a solution A;
step three: slowly adding a silicon source into the solution A under the condition of strong stirring, and continuously stirring to obtain sol B; wherein the rate of slowly adding the silicon source is 0.001-5 mol/min;
step four: putting the sol B into a reaction container, and crystallizing for 6-240 hours at the temperature of 25-85 ℃;
step five: after the reaction is finished, carrying out solid-liquid separation, washing, drying and high-temperature calcination treatment on the solid product to obtain the high-crystallinity nano hierarchical pore X-type molecular sieve;
the alkali source is inorganic alkali source, and M is generated according to theory2Measuring the amount of O, and generating Al by an aluminum source according to a theory2O3Metering of the silicon source to theoretically form SiO2In the amount of N-methyl pyrrolidone NMP for short, and the mol ratio of each component in the sol B is M2O：Al2O3：SiO2：H2O: NMP 1.0-15:1.0:1.8-15:40-450:0.6-13.8, M representing an alkali metal.
2. The method of claim 1, wherein the alkali source is one or more of sodium hydroxide, sodium oxide, and sodium carbonate;
the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, pseudo-boehmite, aluminum oxide, aluminum hydroxide, aluminum carbonate, aluminum powder, aluminum isopropoxide and aluminum acetate.
3. The method according to claim 1, wherein the silicon source is one or more of water glass, silica white, sodium silicate, silica sol, ethyl orthosilicate, silica gel, and diatomite.
4. The method according to claim 1, wherein the stirring speed of the intensive stirring in the third step is 400 to 1500 rpm.
5. The preparation method of claim 1, wherein in the fourth step, the reaction vessel is one or more of a closed polytetrafluoroethylene reaction kettle and a glass flask.
6. The preparation method according to claim 1, wherein in the fourth step, the heating device used at 25-85 ℃ is one or more of an oven, an oil bath, a water bath, a sand bath, an electric heating jacket and a microwave oven, and the crystallization condition is standing or stirring at 200-1000 rpm.
7. The method of claim 1, wherein the high temperature calcination is carried out at a temperature increase rate of 0.2 to 5 ℃ for min-1Heating to 300-700 deg.C, calcining for 0.5-48 h.
8. The high-crystallinity hierarchical pore nanometer X-type molecular sieve prepared by the preparation method of any one of claims 1 to 7 is characterized in that the high-crystallinity hierarchical pore nanometer X-type molecular sieve has a mesoporous structure, the particle diameter is (20-200) nm, and the specific surface area is not less than 420m2 g-1And the external surface area is not less than 50m2 g-1(ii) a The silicon-aluminum ratio is 0.9-1.6.
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