CN113307284A - Preparation method of nanoscale composite molecular sieve - Google Patents
Preparation method of nanoscale composite molecular sieve Download PDFInfo
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- CN113307284A CN113307284A CN202110779108.5A CN202110779108A CN113307284A CN 113307284 A CN113307284 A CN 113307284A CN 202110779108 A CN202110779108 A CN 202110779108A CN 113307284 A CN113307284 A CN 113307284A
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- 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
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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- 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
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- 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
- C01B39/14—Type A
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- 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
- C01B39/22—Type X
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- 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
- C01B39/24—Type Y
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- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The embodiment of the invention provides a preparation method of a nanoscale composite molecular sieve, belonging to the technical field of organic pollutant treatment. The preparation method comprises the following steps: preparing a crystallization liquid of the mesoporous molecular sieve by a hydrothermal synthesis method, wherein the crystallization temperature of the crystallization liquid is 100-200 ℃, and the crystallization time is 0-72 hours; introducing a microporous molecular sieve into the crystallization liquid of the mesoporous molecular sieve, and adding a template agent to fully react; and carrying out suction filtration, washing and drying on the crystallized liquid after reaction. The invention can effectively improve the synergistic effect, shape-selective effect and catalytic performance between the microporous molecular sieve and the mesoporous molecular sieve.
Description
Technical Field
The invention relates to the technical field of organic pollutant treatment, in particular to a preparation method of a nanoscale composite molecular sieve.
Background
The porous material refers to a porous compound and a material mainly containing the porous compound, and has a common characteristic of having a regular and uniform pore structure. Microporous zeolite molecular sieve is used as heterogeneous catalyst in petrochemical industry and other fields, and has wide application range, which is incomparable with mesoporous molecular sieve and macroporous material. The pore size of the microporous zeolite molecular sieve is similar to the size of the molecular sieve used in the field of petrochemical industry, so that the zeolite molecular sieve has certain shape-selective catalytic performance on reactants, reaction products and reaction intermediates, which is not possessed by mesoporous molecular sieves and macroporous materials. However, besides the order of the pore channels, the pore wall composition of the microporous molecular sieve is also ordered on the atomic scale, and is a long-range ordered and short-range ordered crystal structure, while the mesoporous molecular sieve is ordered on the mesoscopic scale (i.e., long-range ordered), but the connection mode among microscopic atoms formed inside the pore wall is disordered and is an amorphous structure, i.e., the mesoporous molecular sieve is long-range ordered and short-range disordered. Therefore, the hydrothermal stability and the thermal stability of the mesoporous molecular sieve are low, and only weak catalytic activity can be provided, so that the application of the mesoporous molecular sieve in the catalytic field, especially in the fields of petrochemical industry and the like with high requirements on the thermal stability of the catalyst, is greatly limited.
In order to solve the above problems, scientists have tried to "make mesopores" inside zeolite molecular sieves by making the most of the pores inside the molecular sieves and improving the accessibility of the reactants in the pores of the molecular sieves. Methods for introducing mesopores into zeolite molecular sieves are various and mainly classified into a template method, a particle stacking method, a post-treatment method and the like. Although the combination of the two different molecular sieves can be improved by mechanical mixing, and there is a certain synergistic effect between the two molecular sieves, the synergistic effect is very limited. The key to solve the problem is whether the two molecular sieves can be compounded together on a nanometer level. Because the particle size of the zeolite molecular sieve prepared in laboratory or in industry is usually in nanometer or micrometer level, the simple mechanical mixing is only macroscopic relative to the zeolite molecular sieve particles, the method is difficult to mix the two molecular sieves uniformly and fully on the micro-nanometer level, thus the synergistic effect of the two molecular sieves is severely limited, and the catalytic efficiency of the whole mixed catalyst is rapidly reduced in advance due to the poor anti-carbon capacity of one molecular sieve. Therefore, the synthesis of composite molecular sieves that are composited at a nanoscale and have different crystal structures has become a research hotspot in the field of new materials.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of a nano-scale composite molecular sieve, aiming at improving the synergistic effect, shape-selective effect and catalytic performance between a microporous molecular sieve and a mesoporous molecular sieve.
The preparation method of the nanoscale composite molecular sieve provided by the embodiment of the invention comprises the following steps:
s10: preparing a crystallization liquid of the mesoporous molecular sieve by a hydrothermal synthesis method, wherein the crystallization temperature of the crystallization liquid is 100-200 ℃, and the crystallization time is 0-72 hours;
s20: introducing a microporous molecular sieve into the crystallization liquid of the mesoporous molecular sieve, and adding a template agent to fully react;
s30: and carrying out suction filtration, washing and drying on the crystallized liquid after reaction.
Further, the aluminum salt of the hydrothermal synthesis method is at least one of sodium metaaluminate, sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum isopropoxide, aluminum sec-butoxide and aluminum acetate; the silicon salt is at least one of silica sol, ethyl orthosilicate, sodium silicate, water glass, silica gel powder, white carbon silicon and silicon dioxide powder.
Further, the crystallization liquid of the mesoporous molecular sieve is at least one of Y-type molecular sieve crystallization liquid, A-type molecular sieve crystallization liquid, X-type molecular sieve crystallization liquid and ZSM-5-type molecular sieve crystallization liquid.
Further, the microporous molecular sieve is a Beta molecular sieve.
Further, the template agent is at least one of ethylamine, propylamine, ethylenediamine, triethylamine, n-butylamine, tetrapropylammonium hydroxide, hexadecylammonium bromide and tetrapropylammonium bromide.
Further, the ratio of the microporous molecular sieve to the mesoporous molecular sieve is between 0 and 30.
Further, the crystallized liquid after the reaction was washed three times with deionized water to obtain a sample.
Further, the sample was dried in an oven at 100 ℃ for 12 hours.
The invention has the beneficial effects that: firstly, according to the preparation method of the nano-scale composite molecular sieve provided by the embodiment of the invention, the microporous molecular sieve is introduced into the crystallization liquid of the mesoporous molecular sieve to form the composite molecular sieve, and the crystallization liquid after reaction is subjected to suction filtration, washing and drying, so that the synergistic effect, the shape-selective effect and the catalytic performance between the microporous molecular sieve and the mesoporous molecular sieve can be effectively improved. Secondly, the composite molecular sieve can shorten the diffusion distance of products between the mesoporous molecular sieve and the microporous molecular sieve and can properly adjust the acidity of the outer surface of the composite molecular sieve. Finally, when the composite molecular sieve is assembled, gaps among crystal grains of the produced molecular sieve can cause a mesoporous or macroporous structure to appear in the composite molecular sieve, which is more beneficial to the molecular transfer and diffusion effects of reactants and products, and achieves the purposes of improving the reaction yield and reducing the occurrence of carbon deposition.
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention will be described in detail and completely with reference to the accompanying drawings. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention.
The terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Example 1
The preparation method of the nanoscale composite molecular sieve provided by the embodiment of the invention can comprise the following steps:
s10: under the action of magnetic stirring, 1g of NaAlO was added to deionized water2Stirring was continued for 30 minutes, to which 0.89g of NaOH was added and stirring was continued until it was completely dissolved in deionized water to form a transparent solution of sodium aluminate.
S20: under the action of magnetic stirring, 12.5g of silica sol was slowly added to the above solution, and after stirring for 120 minutes, 5mL of 0.1mol/L dilute sulfuric acid was added, and stirring was continued for 60 minutes.
S30: and (3) putting the obtained gel solution into a high-temperature high-pressure reaction kettle, transferring the reaction kettle into an oven, crystallizing the reaction kettle at 120 ℃ for 24 hours, and cooling to obtain the mesoporous molecular sieve crystallization liquid.
S40: 5.0g of the mesoporous molecular sieve crystallized liquid obtained after completion of crystallization was placed in a 100 mL beaker, and 5mL of tetraethylammonium hydroxide solution (TEAOH) was added thereto and stirred for 12 hours.
S50: adding 3g of silicon dioxide powder into the solution, continuously stirring for 6 hours, finally dropwise adding a certain amount of concentrated sulfuric acid into the solution to adjust the alkalinity, placing the solution into a reaction kettle containing 100 mL of polytetrafluoroethylene lining after strongly stirring the solution uniformly, transferring the reaction kettle into an oven, and crystallizing the reaction kettle for 24 hours at 140 ℃.
S60: and after the reaction kettle is cooled, carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value of the washing solution is 7, and drying the reaction solution in an oven at 100 ℃ for 12 hours.
Example 2
S10: under the action of magnetic stirring, 1g of NaAlO was added to deionized water2Stirring was continued for 30 minutes, to which 0.89g of NaOH was added and stirring was continued until it was completely dissolved in deionized water to form a transparent solution of sodium aluminate.
S20: under the action of magnetic stirring, 12.5g of silica sol was slowly added to the above solution, and after stirring for 120 minutes, 5mL of 0.1mol/L dilute sulfuric acid was added, and stirring was continued for 60 minutes.
S30: and (3) putting the obtained gel solution into a high-temperature high-pressure reaction kettle, transferring the reaction kettle into an oven, crystallizing the reaction kettle at 120 ℃ for 24 hours, and cooling to obtain the mesoporous molecular sieve crystallization liquid.
S40: 10.0g of the mesoporous molecular sieve crystallized liquid obtained after completion of crystallization was placed in a 100 mL beaker, and 5mL of tetraethylammonium hydroxide solution (TEAOH) was added thereto and stirred for 12 hours.
S50: adding 3g of silicon dioxide powder into the solution, continuously stirring for 6 hours, finally dropwise adding a certain amount of concentrated sulfuric acid into the solution to adjust the alkalinity, placing the solution into a reaction kettle containing 100 mL of polytetrafluoroethylene lining after strongly stirring the solution uniformly, transferring the reaction kettle into an oven, and crystallizing the reaction kettle for 24 hours at 140 ℃.
S60: and after the reaction kettle is cooled, carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value of the washing solution is 7, and drying the reaction solution in an oven at 100 ℃ for 12 hours.
Example 3
S10: under the action of magnetic stirring, 1g of NaAlO was added to deionized water2Stirring was continued for 30 minutes, to which 0.89g of NaOH was added and stirring was continued until it was completely dissolved in deionized water to form a transparent solution of sodium aluminate.
S20: under the action of magnetic stirring, 12.5g of silica sol was slowly added to the above solution, and after stirring for 120 minutes, 5mL of 0.1mol/L dilute sulfuric acid was added, and stirring was continued for 60 minutes.
S30: and (3) putting the obtained gel solution into a high-temperature high-pressure reaction kettle, transferring the reaction kettle into an oven, crystallizing the reaction kettle at 120 ℃ for 24 hours, and cooling to obtain the mesoporous molecular sieve crystallization liquid.
S40: 15.0g of the mesoporous molecular sieve crystallized liquid obtained after completion of crystallization was placed in a 100 mL beaker, and 5mL of tetraethylammonium hydroxide solution (TEAOH) was added thereto and stirred for 12 hours.
S50: adding 3g of silicon dioxide powder into the solution, continuously stirring for 6 hours, finally dropwise adding a certain amount of concentrated sulfuric acid into the solution to adjust the alkalinity, placing the solution into a reaction kettle containing 100 mL of polytetrafluoroethylene lining after strongly stirring the solution uniformly, transferring the reaction kettle into an oven, and crystallizing the reaction kettle for 24 hours at 140 ℃.
S60: and after the reaction kettle is cooled, carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value of the washing solution is 7, and drying the reaction solution in an oven at 100 ℃ for 12 hours.
Example 4
S10: under the action of magnetic stirring, 1g of NaAlO was added to deionized water2Stirring was continued for 30 minutes, to which 0.89g of NaOH was added and stirring was continued until it was completely dissolved in deionized water to form a transparent solution of sodium aluminate.
S20: under the action of magnetic stirring, 12.5g of silica sol was slowly added to the above solution, and after stirring for 120 minutes, 5mL of 0.1mol/L dilute sulfuric acid was added, and stirring was continued for 60 minutes.
S30: and (3) putting the obtained gel solution into a high-temperature high-pressure reaction kettle, transferring the reaction kettle into an oven, crystallizing the reaction kettle at 120 ℃ for 24 hours, and cooling to obtain the mesoporous molecular sieve crystallization liquid.
S40: 20.0g of the mesoporous molecular sieve crystallized liquid obtained after completion of crystallization was placed in a 100 mL beaker, to which 5mL of tetraethylammonium hydroxide solution (TEAOH) was added and stirred for 12 hours.
S50: adding 3g of silicon dioxide powder into the solution, continuously stirring for 6 hours, finally dropwise adding a certain amount of concentrated sulfuric acid into the solution to adjust the alkalinity, placing the solution into a reaction kettle containing 100 mL of polytetrafluoroethylene lining after strongly stirring the solution uniformly, transferring the reaction kettle into an oven, and crystallizing the reaction kettle for 24 hours at 140 ℃.
S60: and after the reaction kettle is cooled, carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value of the washing solution is 7, and drying the reaction solution in an oven at 100 ℃ for 12 hours.
The invention has the beneficial effects that: firstly, according to the preparation method of the nano-scale composite molecular sieve provided by the embodiment of the invention, the microporous molecular sieve is introduced into the crystallization liquid of the mesoporous molecular sieve to form the composite molecular sieve, and the crystallization liquid after reaction is subjected to suction filtration, washing and drying, so that the synergistic effect, the shape-selective effect and the catalytic performance between the microporous molecular sieve and the mesoporous molecular sieve can be effectively improved.
Secondly, the composite molecular sieve can shorten the diffusion distance of products between the mesoporous molecular sieve and the microporous molecular sieve and can properly adjust the acidity of the outer surface of the composite molecular sieve.
Finally, when the composite molecular sieve is assembled, gaps among crystal grains of the produced molecular sieve can cause a mesoporous or macroporous structure to appear in the composite molecular sieve, which is more beneficial to the molecular transfer and diffusion effects of reactants and products, and achieves the purposes of improving the reaction yield and reducing the occurrence of carbon deposition.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a nanoscale composite molecular sieve is characterized by comprising the following steps:
s10: preparing a crystallization liquid of the mesoporous molecular sieve by a hydrothermal synthesis method, wherein the crystallization temperature of the crystallization liquid is 100-200 ℃, and the crystallization time is 0-72 hours;
s20: introducing a microporous molecular sieve into the crystallization liquid of the mesoporous molecular sieve, and adding a template agent to fully react;
s30: and carrying out suction filtration, washing and drying on the crystallized liquid after reaction.
2. The method for preparing the nanoscale composite molecular sieve according to claim 1, wherein the aluminum salt of the hydrothermal synthesis method is at least one of sodium metaaluminate, sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum isopropoxide, aluminum sec-butoxide and aluminum acetate; the silicon salt is at least one of silica sol, ethyl orthosilicate, sodium silicate, water glass, silica gel powder, white carbon silicon and silicon dioxide powder.
3. The method of claim 1, wherein the mesoporous molecular sieve is at least one of a Y-type molecular sieve crystal, an a-type molecular sieve crystal, an X-type molecular sieve crystal, and a ZSM-5-type molecular sieve crystal.
4. The method of claim 1, wherein the microporous molecular sieve is a Beta molecular sieve.
5. The method of claim 1, wherein the template is at least one of ethylamine, propylamine, ethylenediamine, triethylamine, n-butylamine, tetrapropylammonium hydroxide, hexadecylammonium bromide, and tetrapropylammonium bromide.
6. The method of claim 1, wherein the ratio of the microporous molecular sieve to the mesoporous molecular sieve is between 0 and 30.
7. The method of claim 1, wherein in step S30, the crystallized liquid after the reaction is washed with deionized water three times to obtain a sample.
8. The method of claim 7, wherein the sample is dried in an oven at 100 ℃ for 12 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208718A (en) * | 1998-07-01 | 1999-02-24 | 复旦大学 | Composite medium and micro porous molecular sieve and synthesis method therefor |
| US20020090337A1 (en) * | 1999-06-17 | 2002-07-11 | Avelino Corma Canos | Synthesis of zeolites |
| US6669924B1 (en) * | 1999-11-23 | 2003-12-30 | Universite Laval | Mesoporous zeolitic material with microporous crystalline mesopore walls |
| CN101108736A (en) * | 2006-07-21 | 2008-01-23 | 中国石油天然气集团公司 | Method of manufacturing Y type molecular sieve having micropore and mesohole at the same time |
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2021
- 2021-07-09 CN CN202110779108.5A patent/CN113307284A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208718A (en) * | 1998-07-01 | 1999-02-24 | 复旦大学 | Composite medium and micro porous molecular sieve and synthesis method therefor |
| US20020090337A1 (en) * | 1999-06-17 | 2002-07-11 | Avelino Corma Canos | Synthesis of zeolites |
| US6669924B1 (en) * | 1999-11-23 | 2003-12-30 | Universite Laval | Mesoporous zeolitic material with microporous crystalline mesopore walls |
| CN101108736A (en) * | 2006-07-21 | 2008-01-23 | 中国石油天然气集团公司 | Method of manufacturing Y type molecular sieve having micropore and mesohole at the same time |
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Application publication date: 20210827 |