CN107686119B - hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof - Google Patents

hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof Download PDF

Info

Publication number
CN107686119B
CN107686119B CN201610628126.2A CN201610628126A CN107686119B CN 107686119 B CN107686119 B CN 107686119B CN 201610628126 A CN201610628126 A CN 201610628126A CN 107686119 B CN107686119 B CN 107686119B
Authority
CN
China
Prior art keywords
molecular sieve
hierarchical porous
aluminum
mesoporous
silicon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610628126.2A
Other languages
Chinese (zh)
Other versions
CN107686119A (en
Inventor
陈丽华
张春磊
孙明慧
刘豪
程志恒
彭钊
黄丹娅
苏宝连
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University of Technology (WUT)
Original Assignee
Wuhan University of Technology (WUT)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology (WUT) filed Critical Wuhan University of Technology (WUT)
Priority to CN201610628126.2A priority Critical patent/CN107686119B/en
Publication of CN107686119A publication Critical patent/CN107686119A/en
Application granted granted Critical
Publication of CN107686119B publication Critical patent/CN107686119B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C01B39/04—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
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/14—Pore volume
    • 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

Abstract

The invention discloses hierarchical pore silicon aluminum molecular sieve nanoclusters and a preparation method thereof, wherein the hierarchical pore silicon aluminum molecular sieve nanoclusters consist of molecular sieve nanoparticles and contain a mesoporous-microporous hierarchical pore structure, wherein the pore diameter of a mesoporous is 20-30 nm.

Description

hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof
Technical Field
The invention relates to the technical field of molecular sieve synthesis, in particular to hierarchical pore silicon-aluminum molecular sieve nanoclusters and a preparation method thereof.
Background
In recent years, zeolite molecular sieves are used as solid acid catalysts, is widely applied to important fields of petrochemical industry, petroleum cracking, organic macromolecule synthesis and the like, but the pore channel size of micropores of the zeolite molecular sieves greatly limits the material transmission performance of guest molecules in the catalysts, so that macromolecules cannot reach active sites inside the micropores of the molecular sieves, thereby causing the deactivation problem of carbon deposited catalysts in the pores, and further limiting the practical application of the catalysts, and therefore, the improvement of the flow diffusion performance of the zeolite molecular sieves becomes which is an important way for improving the catalytic performance of the zeolite molecular sieves.
The nanometer molecular sieve has intercrystalline pores formed by stacking particles, and has more acid centers on the outer surface and stronger acidity, so that the nanometer molecular sieve has higher reaction activity.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention mainly aims to provide hierarchical pore silicoaluminophosphate molecular sieve nanoclusters and a preparation method thereof, wherein mesoporous/macroporous channels are introduced into a nano molecular sieve, so that the molecular sieve has excellent acid properties, has a hierarchical pore channel structure in the structure, and shows synergistic effect and special catalytic performance in catalytic reaction.
The purpose of the invention is realized by the following technical scheme:
hierarchical porous silicon aluminum molecular sieve nanoclusters are characterized in that the particle size of each hierarchical porous silicon aluminum molecular sieve nanocluster is , the particle size of each hierarchical porous silicon aluminum molecular sieve nanocluster is 1.3-1.8 mu m, the pore volume of each hierarchical porous silicon aluminum molecular sieve nanocluster is the same as that of each molecular sieve nanoparticle, the molecular sieve nanoparticles are 10-20nm in size, each hierarchical porous silicon aluminum molecular sieve nanocluster contains a mesoporous-microporous hierarchical pore structure, and the pore size of each mesoporous is 20-30 nm.
The preparation method of the kinds of hierarchical pore silicon-aluminum molecular sieve nanoclusters comprises the following steps:
1) mixing and fully stirring the structure directing agent, water, an aluminum source, a silicon source and ethanol to obtain a mixed solution, adding a hard template, and aging at room temperature to obtain a dry adhesive;
2) placing the dry glue obtained in the step 1) into a reaction kettle, leaving water at the bottom of the reaction kettle, performing crystallization reaction on the dry glue, and then washing and drying to obtain a hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material;
3) roasting the hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material obtained in the step 2), and removing a carbon template to obtain the hierarchical porous silicon-aluminum molecular sieve nanocluster.
In the scheme, the molecular sieve structure directing agent is tetrapropylammonium hydroxide; the hard template is an ordered macroporous-mesoporous hierarchical porous carbon material, wherein the pore diameter of the macropores and the pore diameter of the mesopores are both adjustable; the pore diameter of the macropores is 200-600 nm, and the pore diameter of the mesopores is 20-40 nm; reference is made to the literature [ chem. mate. 2010, 22, 3433-3440 ].
In the scheme, the silicon source is tetraethyl orthosilicate; the aluminum source is sodium metaaluminate, aluminum isopropoxide or aluminum sulfate.
In the scheme, the aging temperature is 30-60 ℃, and the time is 8-12 h.
In the scheme, the molar ratio of the silicon source, the aluminum source and the structure directing agent is 1 (0.001-0.02) to 0.36-0.8.
In the scheme, the using amount of the hard template is SiO obtained by hydrolyzing a silicon source2Based on the mass of (1), SiO2The weight of the hard template accounts for 3-10% of that of the hard template.
In the scheme, the mass ratio of the water to the dry glue in the step 2) is (1-2) to 1.
In the scheme, the crystallization reaction temperature is 150-200 ℃, and the time is 8-16 h.
In the scheme, the roasting temperature is 500-600 ℃, and the roasting time is 6-8 h.
Compared with the prior art, the invention has the beneficial effects that:
the mesoporous pore canal is introduced into the nano molecular sieve, so that the molecular sieve has the properties different from those of the conventional nano molecular sieve, not only has excellent acid properties, but also introduces a multi-stage distribution pore canal structure in the structure of the molecular sieve, shows synergistic effect and special catalytic performance in catalytic reaction, can improve carbon deposition resistance, improve the diffusion performance of products, and improve the catalytic reaction activity and the selectivity of target products; the obtained hierarchical porous silicon-aluminum molecular sieve nanoclusters have important research and application values in hydrocarbon catalytic conversion and other processes in the field of petrochemical industry.
Drawings
FIG. 1 is a scanning electron micrograph (a, b) and a transmission electron micrograph (c, d) of a multi-stage porous aluminosilicate molecular sieve nanocluster prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of a multigraded-pore aluminosilicate molecular sieve nanocluster prepared in example 2 of the present invention.
FIG. 3 shows a hierarchical porous aluminosilicate molecular sieve nanocluster prepared in example 3 of the present invention (a)29Si NMR spectrum sum (b)27Nuclear magnetic resonance spectrum of Al.
Fig. 4 shows a graph of a nitrogen adsorption-desorption isotherm of the hierarchical porous aluminosilicate molecular sieve nanoclusters prepared in example 4 of the present invention, (b) a micropore size distribution diagram and (c) a mesopore size distribution diagram.
Detailed Description
For a better understanding of the present invention, the following example is provided to illustrate the present invention, but the present invention is not limited to the following example.
In the following examples, the hard template is ordered macroporous-mesoporous hierarchical porous carbon material, and the synthesis method is referred to in the literature [ chem.mater.2010, 22, 3433-.
Example 1
hierarchical porous Si-Al molecular sieve nanoclusters, wherein the molar ratio of a silicon source to an aluminum source to a structure directing agent in the preparation process is 1:0.01:0.36, and the SiO obtained after hydrolysis of the silicon source2Accounting for 3 percent of the mass of the ordered macroporous-mesoporous hierarchical porous carbon material, the method specifically comprises the following steps:
adding 329 mu L of TEOS and 0.00612g of aluminum isopropoxide into a mixed solution of 1.218g of tetrapropylammonium hydroxide aqueous solution (20 wt.%), 1.35g of deionized water and 0.345g of ethanol (Chinese medicine), fully stirring uniformly for 5h, adding 3g of ordered macroporous-mesoporous hierarchical porous carbon material (the pore diameter of the macropore is 400nm and the pore diameter of the mesopore is 20nm) to obtain a mixed solution I, and drying and aging in an oven at 40 ℃ for 10h to obtain dry glue; placing the obtained dry glue in a 150mL reaction kettle, taking 0.2g of deionized water from the bottom of the reaction kettle, heating to 180 ℃, crystallizing for 10 hours, and then washing and drying to obtain a hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material; and finally, heating to 550 ℃ at the speed of 2 ℃/min, preserving the heat for 6 hours, and removing the carbon template to obtain the hierarchical pore silicon-aluminum molecular sieve nanocluster.
FIG. 1(a, b) is a scanning electron micrograph of the product obtained in the present example, and FIG. 1(c, d) is a transmission electron micrograph of the product obtained in the present example, it can be seen from FIG. 1 that the product obtained is composed of size molecular sieve nanoclusters each of which is composed of 10-20nm size molecular sieve nanoparticles.
Example 2
hierarchical porous Si-Al molecular sieve nanoclusters, wherein the molar ratio of a silicon source to an aluminum source to a structure directing agent in the preparation process is 1:0.001:0.5, and the SiO obtained after hydrolysis of the silicon source2Accounting for 5 percent of the mass of the ordered macroporous-mesoporous hierarchical porous carbon material, the method specifically comprises the following steps:
adding 548 mu L of TEOS and 0.00051g of aluminum isopropoxide into a mixed solution of 1.2688g of tetrapropylammonium hydroxide aqueous solution (20 wt.%), 2.25g of deionized water and 4.6g of ethanol (Chinese medicine), fully stirring uniformly for 5h, adding 3g of ordered macroporous-mesoporous hierarchical porous carbon material (the pore diameter of macropores is 400nm, and the pore diameter of mesopores is 20nm) to obtain a mixed solution I, and drying and aging in an oven at 40 ℃ for 10h to obtain dry glue; placing the obtained dry glue in a 100mL reaction kettle, taking 0.2g of deionized water from the bottom of the kettle, heating to 180 ℃, crystallizing for 10 hours, and then washing and drying to obtain a hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material; and finally, heating to 550 ℃ at the speed of 2 ℃/min, preserving the heat for 6 hours, and removing the carbon template to obtain the hierarchical pore silicon-aluminum molecular sieve nanocluster.
Fig. 2 is an XRD chart of the product obtained in this example, which shows five characteristic diffraction peaks of the MFI-type structure molecular sieve at 2 θ of 7.8 °, 8.8 °, 23.2 °, 23.8 °, and 24.3 °, and the peaks are high in intensity, indicating that the degree of crystallinity is high.
Example 3
hierarchical porous Si-Al molecular sieve nanoclusters, wherein the molar ratio of a silicon source to an aluminum source to a structure directing agent in the preparation process is 1:0.005:0.65, and the SiO obtained after hydrolysis of the silicon source2Accounting for 10 percent of the mass of the ordered macroporous-mesoporous hierarchical porous carbon material, the method specifically comprises the following steps:
1095 mu L of TEOS and 0.0051g of aluminum isopropoxide are added into 3.2988g of tetrapropylammonium hydroxide aqueous solution (20 wt.%), 4.5g of deionized water and 4.6g of ethanol (Chinese medicine), the mixture is fully and uniformly stirred for 5h, 3g of ordered macroporous-mesoporous hierarchical porous carbon material (the diameter of a macroporous hole is 400nm, and the diameter of a mesoporous hole is 20nm) is added to obtain a mixed solution I, and the mixed solution I is dried and aged in an oven at 40 ℃ for 10h to obtain dry glue; placing the obtained dry glue in a 150mL reaction kettle, taking 0.2g of deionized water from the bottom of the reaction kettle, heating to 150 ℃, crystallizing for 16h, and then washing and drying to obtain a hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material; and finally, heating to 550 ℃ at the speed of 2 ℃/min, preserving the heat for 6 hours, and removing the carbon template to obtain the hierarchical pore silicon-aluminum molecular sieve nanocluster.
FIGS. 3(a) and 3(b) are schematic diagrams of the multi-stage porous aluminosilicate molecular sieve nanoclusters obtained in this example29Si NMR spectrum and27al nmr spectrum. As is clear from FIG. 3(a), Q was not present in any of the products after crystal transformation2Species (silicon species connecting the two terminal hydroxyl groups, chemical shift at-92 ppm), consisting mainly of Q4Species (fully condensed silicon species not attached to terminal hydroxyl groups) with a small amount of Q present3It can be seen from FIG. 3(b) that the product is substantially present as a four-coordinated aluminum species (chemical shift 54ppm) without the presence of six-coordinated aluminum (chemical shift 0ppm), since the four-coordinated aluminum is in a framework position of the molecular sieve and the six-coordinated aluminum is in a non-framework position of the molecular sieve, indicating that the aluminum in the product after the crystal transformation is substantially present in a four-coordinated manner in the framework of the molecular sieve.
Example 4
hierarchical porous Si-Al molecular sieve nanoclusters, wherein the molar ratio of a silicon source to an aluminum source to a structure directing agent in the preparation process is 1:0.02:0.8, and the SiO obtained after hydrolysis of the silicon source2Accounting for 3 percent of the mass of the ordered macroporous-mesoporous hierarchical porous carbon material, comprises the following steps:
adding 329 mu L of TEOS and 0.00306g of aluminum isopropoxide into a mixed solution of 0.5481g of tetrapropylammonium hydroxide aqueous solution (20 wt.%), 1.35g of deionized water and 2.76g of ethanol (Chinese medicine), fully stirring uniformly for 5h, adding 3g of ordered macroporous-mesoporous hierarchical porous carbon material (the pore diameter of the macropore is 400nm, and the pore diameter of the mesopore is 20nm) to obtain a mixed solution I, and drying and aging in an oven at 60 ℃ for 8h to obtain dry glue; placing the obtained dry glue in a reaction kettle, taking 0.2g of deionized water from the bottom of the reaction kettle, heating to 180 ℃, crystallizing for 10 hours, and then washing and drying to obtain a hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material; and finally, heating to 550 ℃ at the speed of 2 ℃/min, preserving the heat for 6 hours, and removing the carbon template to obtain the hierarchical pore silicon-aluminum molecular sieve nanocluster.
FIG. 4 shows a nitrogen adsorption-desorption isotherm diagram 4(a), a micropore diameter distribution diagram 4(b) and a mesopore diameter distribution diagram 4(c) of the product obtained in the present example. From fig. 4(a), it can be seen that the isothermal adsorption curve of the product has a large adsorption at a relative pressure of less than 0.02, indicating that a large amount of microporous channel structures exist in the product; this shows that hysteresis loops exist in the product when the relative pressure is in the range of 0.7-1, and shows that mesoporous pore channel structures exist in the product. Combining fig. 4(b) and fig. 4(c), it can be seen that the pore diameter of the micropores of the product is mainly concentrated around 0.45nm, and at the same time, the material has a mesoporous structure and the pore diameter distribution is relatively narrow. The BET area of the product was 490m2Per g, specific surface area of micropores 78m2(g) total pore volume of 1.05cm3 step proves that a large amount of mesoporous structures exist in the molecular sieve material, wherein the pore volume generated by mesopores is 1cm3/g。
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (10)

  1. hierarchical porous silica-alumina molecular sieve nanoclusters are characterized in that the particle size of each hierarchical porous silica-alumina molecular sieve nanocluster is and is 1.3-1.8 microns, each hierarchical porous silica-alumina molecular sieve nanocluster is formed by accumulating molecular sieve nanoparticles, wherein the size of each molecular sieve nanoparticle is 10-20nm, each hierarchical porous silica-alumina molecular sieve nanocluster contains a mesoporous-microporous hierarchical pore structure, and the pore size of each mesoporous is 20-30 nm;
    the preparation method comprises the following steps:
    mixing and fully stirring the structure directing agent, water, an aluminum source, a silicon source and ethanol to obtain a mixed solution, adding a hard template, and aging at room temperature to obtain a dry adhesive;
    2) placing the dry glue obtained in the step 1) into a reaction kettle, leaving water at the bottom of the reaction kettle, performing crystallization reaction on the dry glue, and then washing and drying to obtain a hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material;
    3) roasting the hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material obtained in the step 2), and removing a carbon template to obtain the hierarchical porous silicon-aluminum molecular sieve nanocluster.
  2. 2. The method of preparing a multigraded-pore silicoaluminophosphate molecular sieve nanocluster of claim 1, comprising the steps of:
    1) mixing and fully stirring the structure directing agent, water, an aluminum source, a silicon source and ethanol to obtain a mixed solution, adding a hard template, and aging at room temperature to obtain a dry adhesive;
    2) placing the dry glue obtained in the step 1) into a reaction kettle, leaving water at the bottom of the reaction kettle, performing crystallization reaction on the dry glue, and then washing and drying to obtain a hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material;
    3) roasting the hierarchical porous silicon-aluminum molecular sieve/ordered macroporous-mesoporous hierarchical porous carbon mixed material obtained in the step 2), and removing a carbon template to obtain the hierarchical porous silicon-aluminum molecular sieve nanocluster.
  3. 3. The method of claim 2, wherein the structure directing agent is tetrapropylammonium hydroxide; the hard template is an ordered macroporous-mesoporous hierarchical porous carbon material, wherein the pore diameter of the macropores is 200-600 nm, and the pore diameter of the mesopores is 20-40 nm.
  4. 4. The method according to claim 2, wherein the silicon source is tetraethyl orthosilicate; the aluminum source is sodium metaaluminate, aluminum isopropoxide or aluminum sulfate.
  5. 5. The method of claim 2, wherein the molar ratio of the Si source, the Al source and the structure-directing agent in step 1) is 1 (0.001-0.02) to 0.36-0.82.
  6. 6. The method according to claim 2, wherein the hard template is used in an amount corresponding to SiO obtained by hydrolysis of a silicon source2Based on the mass of (1), SiO2The weight of the hard template accounts for 3-10% of that of the hard template.
  7. 7. The preparation method of the adhesive composition, according to claim 2, wherein the mass ratio of the water to the dry adhesive in the step 2) is (1-2): 1.
  8. 8. The method according to claim 2, wherein the crystallization reaction temperature is 150-200 ℃ and the crystallization reaction time is 8-16 h.
  9. 9. The preparation method according to claim 2, wherein the roasting temperature is 500-600 ℃ and the roasting time is 6-8 h.
  10. 10. The method according to claim 2, wherein the aging temperature is 30 to 60 ℃ and the aging time is 8 to 12 hours.
CN201610628126.2A 2016-08-03 2016-08-03 hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof Active CN107686119B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610628126.2A CN107686119B (en) 2016-08-03 2016-08-03 hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610628126.2A CN107686119B (en) 2016-08-03 2016-08-03 hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107686119A CN107686119A (en) 2018-02-13
CN107686119B true CN107686119B (en) 2020-01-31

Family

ID=61151373

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610628126.2A Active CN107686119B (en) 2016-08-03 2016-08-03 hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107686119B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116102030A (en) * 2022-12-27 2023-05-12 瑞声科技（南京）有限公司 Molecular sieve material for sound absorption and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100480183C (en) * 2007-01-09 2009-04-22 大连理工大学 Mesoporous-microporous composite material and synthesis method thereof
CN100556800C (en) * 2007-03-08 2009-11-04 复旦大学 A kind of multilevel ordered mesoporous/macropore complex carbon material and preparation method thereof
CN102826565B (en) * 2012-09-05 2014-08-20 北京化工大学 Preparation method of multi-stage pore channel beta molecular screen

Also Published As

Publication number Publication date
CN107686119A (en) 2018-02-13

Similar Documents

Publication Publication Date Title
JP5689890B2 (en) Method for producing ZSM-5 zeolite using nanocrystalline ZSM-5 core
CN103447078B (en) A kind of nano MFI-type molecular sieve with hierarchical pore structure and its preparation method and application
Zhang et al. Facile fabrication of mesopore-containing ZSM-5 zeolite from spent zeolite catalyst for methanol to propylene reaction
Sabarish et al. Synthesis, characterization and evaluations of micro/mesoporous ZSM-5 zeolite using starch as bio template
US20120165558A1 (en) Regularly stacked multilamellar and randomly aligned unilamellar zeolite nanosheets, and their analogue materials whose framework thickness were corresponding to one unit cell size or less than 10 unit cell size
WO2012005449A2 (en) Zeolite or an analogous material thereof including mesopores arranged regularly or irregularly, and preparation method for same
MX2010005333A (en) Process for altering the physico-chemical properties of faujasite y-type zeolites.
CN111115651B (en) Nano molecular sieve, synthesis method and application thereof
WO2018205841A1 (en) Method for preparing mesoporous nay-type zeolite molecular sieve
US11229898B2 (en) Nanometer-size zeolitic particles and method for the production thereof
CN107128947A (en) A kind of preparation method of the middle zeolite molecular sieves of micro-diplopore ZSM 5
CN107074565B (en) Zeolite material having outstanding macroporosity in single crystal and method for producing same
CN107651693B (en) A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve
CN112794338A (en) ZSM-5 molecular sieve and preparation method and application thereof
Moradiyan et al. Ultrasonic-assisted hydrothermal synthesis and catalytic behavior of a novel SAPO-34/Clinoptilolite nanocomposite catalyst for high propylene demand in MTO process
KR101451902B1 (en) Zeolite with MRE structure and their analogue materials possessing mesopore, and synthesis method thereof
JPH0859223A (en) Micro to intermediate fine hole gel and its preparation
CN107686119B (en) hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof
CN107840349B (en) Preparation method of nano ZSM-5 hierarchical pore aggregate
CN106283187B (en) A kind of mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline of ordered big hole-with opal structural and its synthetic method
CN108975351B (en) Preparation method of hierarchical pore ZSM-5 zeolite microspheres
Zhang et al. Synthesis of hierarchical ZSM-5 composed of nanocrystals without a secondary template
Lei et al. Zeolite beta monoliths with hierarchical porosity by the transformation of bimodal pore silica gel
RU2650897C1 (en) Method for producing micro-mesoporous zeolite y and zeolite obtained by this method
CN111689505A (en) Preparation method of ZSM-5 molecular sieve with mesoporous-microporous hierarchical structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant