CN110422855B - Preparation method of Ti-beta molecular sieve nanocrystal - Google Patents
Preparation method of Ti-beta molecular sieve nanocrystal Download PDFInfo
- Publication number
- CN110422855B CN110422855B CN201910678780.8A CN201910678780A CN110422855B CN 110422855 B CN110422855 B CN 110422855B CN 201910678780 A CN201910678780 A CN 201910678780A CN 110422855 B CN110422855 B CN 110422855B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- beta molecular
- nanocrystal
- crystallization
- mixed solution
- 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
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- 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
-
- 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
- C01B39/06—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
- C01B39/08—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 the aluminium atoms being wholly replaced
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of Ti-beta molecular sieve nano-crystal, which comprises the following steps: mixing 0.017-0.062 g of tetrabutyl titanate and 4.21-18 g of solution with the mass fraction of tetraethylammonium hydroxide being 35% to prepare a mixed solution; drying at the temperature of 40-90 ℃ for 30-720 min, uniformly mixing the dried mixed solution with 0.8-7 g of white carbon black, and performing crystallization treatment to obtain a crystallization treatment product; and cooling, washing, drying and calcining the crystallized product in sequence to obtain the Ti-beta molecular sieve nanocrystal with high crystallinity. The method has the advantages of simple synthesis steps, no need of using seed crystals and introducing F ions, complete crystallization in a short time, good dispersity of the prepared Ti-beta molecular sieve nanocrystals and uniform particle size distribution, and small usage amount of the structure-directing agent and water in the synthesis process, so the method has the advantages of low cost, small environmental pollution, contribution to industrial production and the like.
Description
Technical Field
The invention belongs to the technical field of molecular sieve nanocrystals, and particularly relates to a preparation method of a Ti-beta molecular sieve nanocrystal.
Background
The traditional zeolite has the advantages of uniform micropores, rich surface acid points, large specific surface area, good hydrothermal stability and the like, and is widely applied to the aspects of adsorption, heterogeneous catalysis, molecular separation and the like. However, since the pore diameter of zeolite is generally less than 0.7nm, when a catalyst for macromolecular reaction is involved, its diffusion limitation in the crystal is a very serious problem. The nanometer molecular sieve can be prepared, and the diffusion path length is shortened, so that the problem is solved. At present, the nano molecular sieve is widely applied to the traditional fields of adsorbents, heterogeneous catalysis, molecular separation and the like, and the application of the nano molecular sieve is also expanded to the emerging fields of microbial fuel cells, chemical sensing, cosmetics and foods, optical devices, biomedicine, drug delivery and the like.
The nanometer molecular sieve is generally prepared by a conventional hydrothermal crystallization synthesis method, and compared with the conventional micron zeolite, the preparation synthesis process is complex, F ions or crystal seeds need to be introduced, the water consumption is large, the product is difficult to filter and collect, the production cost is high, the wastewater treatment is difficult, and the large-scale production is difficult to form.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of Ti-beta molecular sieve nanocrystal.
In order to realize the technical purpose, the invention is realized according to the following technical scheme:
a preparation method of Ti-beta molecular sieve nanocrystal comprises the following steps:
mixing 0.017-0.062 g of tetrabutyl titanate and 4.21-18 g of solution with the mass fraction of tetraethylammonium hydroxide being 35% to prepare a mixed solution, and drying the mixed solution at the temperature of 40-90 ℃ for 30-720 min;
uniformly mixing the dried mixed solution with 0.8-7 g of white carbon black, and performing crystallization treatment under the steam-assisted condition to obtain a crystallization treatment product;
and cooling, washing, drying and calcining the crystallized product in sequence to obtain the Ti-beta molecular sieve nanocrystal with high crystallinity.
Further, after tetrabutyl titanate and tetraethyl ammonium hydroxide solution are mixed, stirring is carried out for 1-24 h at the stirring speed of 450-550 r/min, and then drying is carried out for 30-720 min at the temperature of 40-90 ℃ to obtain the mixed solution.
Further, the crystallization treatment is carried out in a hydrothermal reaction kettle, and 1-10 ml of deionized water is put into a kettle liner of the hydrothermal reaction kettle.
Further, the mixture is placed into an open glass vessel, and then the glass vessel is placed into a kettle liner of the hydrothermal reaction kettle, and water in the kettle liner of the hydrothermal reaction kettle is prevented from entering the glass vessel.
Further, the crystallization temperature of the crystallization treatment is 130-200 ℃, and the crystallization time is 20-48 h.
Further, the washing treatment comprises: and carrying out centrifugal washing treatment on the liquid gel product, wherein the washing times are 1-3 times, and the centrifugal rotating speed is 8000-12000 r/min.
Further, the calcining temperature of the calcining treatment is 500-600 ℃, and the calcining time is 6-12 hours.
Furthermore, the particle size of the Ti-beta molecular sieve nanocrystal is 40-110 nm.
The preparation method of the Ti-beta molecular sieve nanocrystal provided by the invention has the advantages of simple synthesis steps, no need of using seed crystals and introducing F ions, complete crystallization in a short time, good dispersibility of the prepared Ti-beta molecular sieve nanocrystal and uniform particle size distribution, and small usage of a structure directing agent and water in the synthesis process.
Drawings
FIG. 1 is an XRD pattern of Ti-beta molecular sieve nanocrystals prepared in exemplary example 1 of the present invention;
FIG. 2 is an SEM photograph of Ti-beta molecular sieve nanocrystals prepared in exemplary example 1 of the present invention;
FIG. 3 is an XRD pattern of Ti-beta molecular sieve nanocrystals prepared in exemplary example 2 of the present invention;
FIG. 4 is an SEM photograph of Ti-beta molecular sieve nanocrystals prepared in exemplary example 2 of the present invention;
FIG. 5 is an XRD pattern of Ti-beta molecular sieve nanocrystals prepared in exemplary embodiment 3 of the present invention;
FIG. 6 is an SEM photograph of Ti-beta molecular sieve nanocrystals prepared in exemplary example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be described in more detail below with reference to the accompanying drawings in the preferred embodiments of the present invention. In the drawings, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The described embodiments are only some, but not all embodiments of the invention. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
A preparation method of Ti-beta molecular sieve nanocrystal comprises the following steps:
(1) mixing 0.017-0.062 g of tetrabutyl titanate and 4.21-18 g of solution with the weight percentage of tetraethylammonium hydroxide of 35%, stirring at the stirring speed of 450-550 r/min for 1-24 h, and drying at 40-90 ℃ for 30-720 min to prepare a mixed solution;
(2) uniformly mixing the mixed solution and 0.8-7 g of white carbon black, transferring the mixture and placing the mixture in an open glass vessel, then placing the glass vessel in a hydrothermal reaction kettle liner filled with 1-10 ml of deionized water in a kettle liner, and preventing water outside the glass vessel from entering the glass vessel; under the steam-assisted condition, adjusting the temperature of the hydrothermal reaction kettle to 130-200 ℃, and crystallizing for 20-48 hours to obtain a crystallization treatment product;
(3) naturally cooling the crystallized product to room temperature, washing the crystallized product for 1-3 times in a centrifuge with the centrifugal rotation speed of 8000-12000 r/min, drying, and calcining for 6-12 hours at the temperature of 500-600 ℃ in an air atmosphere to obtain the Ti-beta molecular sieve nanocrystal with high crystallinity and the particle size of 40-110 nm.
The preparation method of the Ti-beta molecular sieve nanocrystal provided by the invention has the advantages that the synthesis steps are simple, seed crystals are not required to be used, F ions are not required to be introduced, the completely crystallized Ti-beta molecular sieve nanocrystal can be prepared in a short time (the crystallization time is short, the crystallization can be carried out within 15h at the shortest time), the prepared Ti-beta molecular sieve nanocrystal has good dispersibility and uniform particle size distribution, and the particle size of the Ti-beta molecular sieve nanocrystal is controlled by controlling parameters during crystallization treatment; meanwhile, different from the traditional xerogel conversion method, the reactant is kept with a small amount of water to enable the nanocrystal to be rapidly formed, so that on one hand, the loss of a structure directing agent (tetraethylammonium hydroxide solution) caused by complete evaporation is prevented, and on the other hand, the small amount of water is beneficial to improving the supersaturation degree and is beneficial to large-scale nucleation and crystal growth.
Example 1
A preparation method of Ti-beta molecular sieve nanocrystal comprises the following steps:
(1) mixing 0.017g of tetrabutyl titanate and 4.21g of solution with the weight percentage of tetraethylammonium hydroxide of 35 percent, stirring at the stirring speed of 500r/min for 12 hours, and drying in an oven at 70 ℃ for 120 minutes to prepare a mixed solution;
(2) uniformly mixing the mixed solution and 0.8g of white carbon black, transferring the mixture and placing the mixture in an open glass vessel, then placing the glass vessel in a hydrothermal reaction kettle liner filled with 4ml of deionized water in a kettle liner, and preventing water outside the glass vessel from entering the glass vessel; under the steam-assisted condition, the temperature of the hydrothermal reaction kettle is adjusted to 160 ℃, and the crystallization time is 20 hours, so as to obtain a crystallization treatment product;
(3) naturally cooling the crystallized product to room temperature, washing the crystallized product for 2 times in a centrifuge with the centrifugal speed of 10000r/min, drying, and finally calcining for 12 hours at 580 ℃ in air atmosphere to obtain the Ti-beta molecular sieve nanocrystal with high crystallinity and the particle size of about 100 nm.
As can be seen from figure 1, a characteristic beta peak appears to prove that Ti-beta is successfully crystallized, and as can be seen from figure 2, the Ti-beta has complete morphology and uniform particle size distribution, and is basically about 100 nm.
Example 2
A preparation method of Ti-beta molecular sieve nanocrystal comprises the following steps:
(1) mixing 0.04g of tetrabutyl titanate and 8.42g of solution with the mass fraction of tetraethylammonium hydroxide of 35 percent, stirring at the stirring speed of 450r/min for 11h, and drying in an oven at 65 ℃ for 180min to prepare a mixed solution;
(2) uniformly mixing the mixed solution with 6g of white carbon black, transferring the mixed solution into a glass bottle, transferring the mixed solution into a 50ml hydrothermal reaction kettle liner, adding 4ml of deionized water into the reaction kettle liner, preventing water outside the glass bottle from entering the glass bottle, adjusting the temperature of the reaction kettle, and crystallizing the mixed solution at 155 ℃ for 48 hours to obtain a crystallization treatment product;
(3) naturally cooling the crystallized product to room temperature, washing the crystallized product for 1 time in a centrifuge with the centrifugal speed of 8000r/min, drying, and calcining for 6 hours at the temperature of 500 ℃ in the air atmosphere to obtain the Ti-beta molecular sieve nanocrystal with high crystallinity and the particle size of about 50 nm.
As can be seen from FIG. 3, there is a characteristic peak of beta, which proves the successful crystallization of Ti-beta, and as can be seen from FIG. 4, Ti-beta has complete morphology and uniform particle size distribution, which is basically around 50 nm.
Example 3
A preparation method of Ti-beta molecular sieve nanocrystal comprises the following steps:
(1) mixing 0.062g of tetrabutyl titanate with 10g of a solution with the weight fraction of tetraethylammonium hydroxide of 35 percent, stirring at the stirring speed of 550r/min for 24 hours, and drying in an oven at the temperature of 90 ℃ for 720 minutes to prepare a mixed solution;
(2) uniformly mixing the mixed solution with 7g of white carbon black, transferring the mixture into an open glass vessel, putting the glass vessel into a hydrothermal reaction kettle liner filled with 4ml of deionized water in the kettle liner, and preventing water outside the glass vessel from entering the glass vessel; under the steam-assisted condition, the temperature of the hydrothermal reaction kettle is adjusted to 165 ℃, and the crystallization time is 24 hours, so as to obtain a crystallization treatment product;
(3) naturally cooling the crystallized product to room temperature, washing the crystallized product in a centrifuge with the centrifugal speed of 12000r/min for 3 times, drying, and calcining at 600 ℃ for 12 hours in air atmosphere to obtain the Ti-beta molecular sieve nanocrystal with high crystallinity and the particle size of about 100 nanometers.
As can be seen from FIG. 5, there is a characteristic peak of beta, which proves the successful crystallization of Ti-beta, and as can be seen from FIG. 6, Ti-beta has complete morphology and uniform particle size distribution, which is basically about 100 nm.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of Ti-beta molecular sieve nanocrystal is characterized by comprising the following steps:
mixing 0.017-0.062 g of tetrabutyl titanate and 4.21-18 g of solution with the mass fraction of tetraethylammonium hydroxide being 35% to prepare a mixed solution, and drying at the temperature of 40-90 ℃ for 30-720 min to obtain the mixed solution;
uniformly mixing the mixed solution with 0.8-7 g of white carbon black to obtain a mixture, and performing crystallization treatment under the steam-assisted condition to obtain a crystallization treatment product;
and cooling, washing, drying and calcining the crystallized product in sequence to obtain the Ti-beta molecular sieve nanocrystal with high crystallinity.
2. The method for preparing Ti-beta molecular sieve nanocrystal, as recited in claim 1, is characterized in that, after tetrabutyl titanate and tetraethyl ammonium hydroxide solution are mixed, the mixture is stirred for 1-24 hours at a stirring speed of 450-550 r/min, and then dried for 30-720 minutes at 40-90 ℃ to obtain a mixed solution.
3. The method for preparing the Ti-beta molecular sieve nanocrystal, as recited in claim 1, wherein the crystallization is performed in a hydrothermal reaction kettle, and 1-10 ml of deionized water is placed in a kettle liner of the hydrothermal reaction kettle.
4. The method of claim 3, wherein the mixture is placed in an open glass vessel, and then the glass vessel is placed in a hydrothermal reaction kettle liner, and water in the hydrothermal reaction kettle liner is prevented from entering the glass vessel.
5. The method for preparing Ti-beta molecular sieve nanocrystal according to claim 1, wherein the crystallization temperature of the crystallization treatment is 130-200 ℃ and the crystallization time is 20-48 h.
6. The method for preparing Ti-beta molecular sieve nanocrystal, according to claim 1, wherein the washing treatment comprises: and carrying out centrifugal washing treatment on the liquid gel product, wherein the washing times are 1-3 times, and the centrifugal rotating speed is 8000-12000 r/min.
7. The method for preparing Ti-beta molecular sieve nanocrystals, as recited in claim 1, wherein the calcination temperature is 500-600 ℃ and the calcination time is 6-12 hours.
8. The method for preparing Ti-beta molecular sieve nanocrystal, as recited in claim 1, wherein the particle size of Ti-beta molecular sieve nanocrystal is 40-110 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910678780.8A CN110422855B (en) | 2019-07-25 | 2019-07-25 | Preparation method of Ti-beta molecular sieve nanocrystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910678780.8A CN110422855B (en) | 2019-07-25 | 2019-07-25 | Preparation method of Ti-beta molecular sieve nanocrystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110422855A CN110422855A (en) | 2019-11-08 |
| CN110422855B true CN110422855B (en) | 2021-04-13 |
Family
ID=68410870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910678780.8A Active CN110422855B (en) | 2019-07-25 | 2019-07-25 | Preparation method of Ti-beta molecular sieve nanocrystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110422855B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111439756A (en) * | 2020-04-07 | 2020-07-24 | 福州大学 | Preparation method of cascade pore heteroatom M-Beta molecular sieve |
| CN113264558B (en) * | 2021-04-15 | 2023-08-22 | 大连理工大学盘锦产业技术研究院 | Fe (Fe) 3 O 4 Preparation method and application of silica-1 molecular sieve nanocrystalline composite material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9108190B1 (en) * | 2012-09-12 | 2015-08-18 | University Of Massachusetts | Rapid synthesis of beta zeolites |
| CN109467099A (en) * | 2019-01-08 | 2019-03-15 | 福州大学 | A kind of preparation method of nanoscale pure silicon step hole Beta molecular sieve |
| CN109850914A (en) * | 2019-04-15 | 2019-06-07 | 福州大学 | A kind of preparation method of the nanoscale without aluminium Ti-Beta molecular sieve |
-
2019
- 2019-07-25 CN CN201910678780.8A patent/CN110422855B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110422855A (en) | 2019-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110422857B (en) | Preparation method of Sn-beta molecular sieve nanocrystal | |
| CN110422855B (en) | Preparation method of Ti-beta molecular sieve nanocrystal | |
| US10099932B2 (en) | Rapid synthesis method of small-crystal-grain ZSM-5 molecular sieve | |
| CN107915234A (en) | A kind of preparation method of 1 nano zeolite aggregation molecular sieves of multi-stage porous TS | |
| CN113233472B (en) | Synthesis method of nano small-grain ZSM-22 molecular sieve | |
| WO2018205841A1 (en) | Method for preparing mesoporous nay-type zeolite molecular sieve | |
| CN112678842A (en) | Synthesis method of nano Sn-Beta molecular sieve | |
| CN108275698B (en) | Beta/ZSM-12 intergrowth zeolite molecular sieve and preparation method thereof | |
| CN106268928B (en) | A kind of ordered big hole-is mesoporous-synthetic method of micropore multistage pore catalyst | |
| Li et al. | Zeolite crystallization in crosslinked chitosan hydrogels: Crystal size control and chitosan removal | |
| CN110422854B (en) | Preparation method of pure silicon beta molecular sieve nanocrystal | |
| CN109999774B (en) | Preparation method of nano titanium dioxide/gamma-alumina composite material powder | |
| US11434140B2 (en) | Hierarchical zeolites and preparation method therefor | |
| CN115893483B (en) | Hollow cage-shaped eighteen-surface SrTiO 3 Preparation method and application thereof | |
| CN114931969B (en) | Ferroferric oxide-ZSM-5 composite material and preparation method and application thereof | |
| CN109368654A (en) | A kind of preparation method of nano Si licalite-1 molecular sieve | |
| JP4314077B2 (en) | Silica and production method thereof | |
| CN113578296B (en) | Lamellar gray TiO2 photocatalytic material and preparation method thereof | |
| CN109772283B (en) | Titanium dioxide photocatalyst and preparation method thereof | |
| CN112723374B (en) | NaY molecular sieve and synthesis method thereof | |
| WO2018218736A1 (en) | Aluminosilicate zeolite molecular sieve having bog structure and preparation method therefor | |
| CN111186846B (en) | ITH structure silicon-aluminum molecular sieve and preparation method thereof | |
| JP4314076B2 (en) | Silica and production method thereof | |
| CN111097293A (en) | Preparation method of MFI molecular sieve membrane material | |
| CN110683558A (en) | Synthesis method of MTT zeolite molecular sieve with short shaft morphology |
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 |