CN107840349B - Preparation method of nano ZSM-5 hierarchical pore aggregate - Google Patents
Preparation method of nano ZSM-5 hierarchical pore aggregate Download PDFInfo
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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
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- 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
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- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention belongs to the technical field of zeolite molecular sieve synthesis, and particularly relates to a ZSM-5 hierarchical pore aggregate formed by aggregating nano zeolite grains. Meanwhile, the aggregate has a mesoporous structure with the aperture of 3-6nm due to the stacking effect, so that the aggregate has the characteristic of hierarchical pores and comprises a micro-mesoporous structure. The aggregate particle size is 2-5 μm, and the ZSM-5 nano-particle size is 80-150 nm. The invention uses industrial cheap silica sol and silica powder as raw materials, adds a silanization reagent, adopts high-throughput equipment and a one-step synthesis method to prepare the silica sol in a hydrothermal system. The obtained product has the advantages of reduced diffusion resistance, shortened diffusion path, etc. The preparation method is simple, easy to industrialize and high in repeatability.
Description
Technical Field
The invention belongs to the technical field of zeolite molecular sieve synthesis, and particularly relates to a preparation method of a nano ZSM-5 hierarchical pore aggregate.
Background
ZSM-5 zeolites belong to the second generation of zeolites, having a typical MFI structure. Due to the special two-dimensional straight pore channel system and the cross pore channel structure, the ZSM-5 has been gradually developed into the first-choice catalytic material in the field of petrochemical industry due to higher hydrothermal stability, shape selectivity and oleophilic and hydrophobic capabilities. The multi-stage pore zeolite has three-dimensional cross-linking in crystal or grain, so that the diffusion, catalytic activity, shape selectivity and reaction life are greatly improved, and the multi-stage pore zeolite is widely concerned.
CN201310384533.X discloses a preparation method of a ZSM-5 type medium-and-micro double-hole composite molecular sieve. The method comprises the following steps of mixing NaAlO2Dissolving TEOS in water, and stirring to obtain a clear solution; gradually dropwise adding TEAOH into the clear solution; loading the obtained mixed solution into a stainless steel high-pressure reaction kettle, and carrying out reaction under a homogeneous phase condition; cooling the reaction kettle to room temperature, and dropwise adding CTAB and H into the product2Mixing the mixed solution of O and stirring; dripping EtOH and stirring; putting the product into a stainless steel high-pressure reaction kettle, and carrying out hydrothermal synthesis reaction; and repeatedly washing, centrifugally extracting and drying the product, and calcining the dried product in a muffle furnace to obtain the ZSM-5 type medium-micro double-hole composite molecular sieve.
CN201010543142.4 relates to a method for synthesizing a microporous-mesoporous composite ZSM-5/MCM-41 molecular sieve; adding ZSM-5 microporous molecular sieve into an acid or alkali solution, wherein the concentration of hydrogen ions in the acid solution is 0.1-1.0 mol/L, and the concentration of hydroxide ions in the alkali solution is 0.1-0.5 mol/L; the liquid-solid mass ratio is 30; dissolving CTAB in water, adding a silicon source or a silicon source and an aluminum source to obtain a clear solution, adding ZSM-5 etched by acid or alkali treatment, adjusting the pH value by using 2mol/L sulfuric acid, crystallizing, filtering, drying and roasting; the mass ratio of ZSM-5 to CTAB is 0.08-0.39; the molar ratio of SiO2, CTAB and H2O in the synthetic gel system is 1: 0.15: 60-120.
CN201310226158.6 discloses a preparation method of a porous silica/ZSM-5 molecular sieve catalyst, belonging to the technical field of shape-selective catalysis. Firstly dispersing a ZSM-5 molecular sieve in ethanol, adding purified nano attapulgite into a hydrophilic organic solvent, slowly adding the purified nano attapulgite into ethanol dispersion of the ZSM-5 molecular sieve to prepare an attapulgite/ZSM-5 molecular sieve, and finally placing the prepared attapulgite/ZSM-5 molecular sieve in iodine vapor to prepare the porous silica/ZSM-5 molecular sieve catalyst.
CN201110320472.1 relates to a preparation method of a step hole ZSM-5 zeolite composite material-based FCC gasoline low-temperature sulfur transfer catalyst. The method comprises the following steps: mixing deionized water, an alkali source and a matrix, adding an aluminum source, a microporous template agent and a silicon source, uniformly stirring to obtain an initial sol mixed system, adding a mesoporous template agent, uniformly stirring, aging, and performing hydrothermal crystallization; cleaning, washing, separating, drying and roasting the product of the hydrothermal crystallization to obtain a step hole ZSM-5 zeolite composite material; carrying out ammonium exchange treatment on the step hole ZSM-5 zeolite composite material, and obtaining a hydrogen type step hole ZSM-5 zeolite composite material through cleaning, washing, separating, drying and roasting; the auxiliary agent and the active component are dipped on the hydrogen type step hole ZSM-5 zeolite composite material step by adopting an equal volume dipping method, and the FCC gasoline low-temperature sulfur transfer catalyst based on the step hole ZSM-5 zeolite composite material is obtained after drying, drying and roasting at room temperature.
The method disclosed by the patent has the defects of complicated steps, poor repeatability, difficulty in industrialization and the like. Therefore, a new method for preparing nano ZSM-5 hierarchical pore aggregates is particularly needed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel method for preparing the hierarchical pore ZSM-5 molecular sieve, which uses industrial cheap silica sol and silica powder as raw materials, adds a silanization reagent, adopts high-throughput equipment and adopts a one-step synthesis method to prepare the hierarchical pore ZSM-5 molecular sieve in a hydrothermal system. The method solves the problem of solid/liquid phase separation in the industrial production of nano zeolite with different particle sizes obtained by the prior art, and solves the problems of complicated preparation process, long crystallization time, higher cost, large environmental pollution and difficult industrialization of the hierarchical pore ZSM-5 zeolite molecular sieve.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing a nano ZSM-5 hierarchical pore aggregate comprises the following steps:
(1) water, T, Al source, Si source and R1And R2Adding the mixture into a reaction kettle, wherein the materials in a molar ratio are as follows: h2O/SiO2＝5-1000，T/SiO2＝0.1-200，Si/Al＝50-∞，R1/SiO2＝0.1-200，R2/SiO2Aging the gel for 0.01-10 hours; the T is a template agent, and the R is1Is a silylating agent, said R2Is a hydroxide;
(2) stirring and crystallizing;
(3) washing, centrifuging and drying to obtain a ZSM-5 nano zeolite aggregate;
the silanization reagent is at least one selected from Dichlorodimethylsilane (DMCS), Trimethylchlorosilane (TMCS) and Hexamethyldisilazane (HMDS); the method comprises the following steps of firstly adding water, a template agent and an aluminum source into a reaction kettle, then gradually and gradually adding a silicon source in the stirring process, and finally adding a silylation agent and hydroxide.
The stirring crystallization is specifically realized by crystallizing for 1-15 days at 60-300 ℃ under the stirring of 50-1000rpm, and cooling to room temperature.
The template agent is at least one selected from n-propylamine, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide and diethanolamine.
The silicon source is at least one selected from silica sol or amorphous silica powder.
The aluminum source is at least one selected from aluminum sulfate octadecahydrate, aluminum isopropoxide or metaaluminate and aluminate.
The crystallization temperature is 100-2＝0.1-50, and the crystallization time is 1-3 days.
Said H2O/SiO2＝5-500。
The T/SiO2＝0.1-50。
The method mainly uses different silanization reagents, proper material proportion and dynamic crystallization to prepare the hierarchical porous ZSM-5 molecular sieve. The method can improve the synthesis efficiency, shorten the crystallization time and have better practicability and effectiveness. The method for synthesizing the molecular sieve obtains unexpected technical effects, avoids the problems that the nano zeolite is easy to agglomerate and difficult to recover and filter in the traditional preparation method, is more suitable for industrialization, and is simple, convenient and feasible. The obtained product has the advantages of reduced diffusion resistance, shortened diffusion path, etc. The invention has the characteristics of simple preparation method, easy industrialization and high repeatability.
The following example further illustrates a novel process for preparing a hierarchical pore ZSM-5 molecular sieve, in accordance with the present invention.
Detailed Description
According to the invention, different silanization reagents are used, the proportion of a template agent to a silicon source to an aluminum source is adjusted, stirring is carried out in the crystallization process, ZSM-5 nano zeolite aggregates with different particle sizes are obtained, and meanwhile, due to the stacking effect, the aggregates have a mesoporous structure with the pore diameter of 3-6nm, so that the aggregates have the characteristic of hierarchical pores and comprise micro-mesoporous structures.
The method comprises the following steps:
(1) water, T, Al source, Si source and R1And R2Adding the mixture into a reaction kettle, wherein the materials in a molar ratio are as follows: h2O/SiO2＝5-1000，T/SiO2＝0.1-200，Si/Al＝50-∞，R1/SiO2＝0.1-200，R2/SiO2Aging the gel for 0.01-10 hours; the T is a template agent, and the R is1Is a silylating agent, said R2Is a hydroxide;
wherein, the water is preferably deionized water;
the templating agent is selected from the group consisting of n-propylamine, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, diethanolamine, and in one embodiment of the present invention, the templating agent is tetrapropylammonium hydroxide; T/SiO20.1 to 50, preferably, T/SiO2＝0.1-30；
The aluminum source is at least one selected from aluminum sulfate octadecahydrate, aluminum isopropoxide or metaaluminate and aluminate, and in one embodiment of the invention, the aluminum source is aluminum sulfate octadecahydrate; Si/Al is 50- ∞, preferably Si/Al is 100-;
the silicon source is at least one selected from silica sol or amorphous silica powder, and H2O/SiO2(iii) 5 to 500, preferably, H2O/SiO2＝5-100；
The silanization reagent is at least one selected from Dichlorodimethylsilane (DMCS), Trimethylchlorosilane (TMCS) and Hexamethyldisilazane (HMDS), preferably Dichlorodimethylsilane (DMCS) or Trimethylchlorosilane (TMCS); r1Where 0.1-200 of/SiO 2 is preferable, R10.2-50% of/SiO 2; the silylating agent helps to form hierarchical pores, and in particular, the silylating agent forms covalent bonds with the silicon source to help form silicon source micelles, thereby helping to form the hierarchical pore nano ZSM-5 molecular sieve.
The hydroxide is sodium hydroxide or potassium hydroxide and is used to control the alkalinity of the system, and in one embodiment of the invention, the hydroxide is sodium hydroxide.
In the charging sequence, preferably, the water, the template agent and the aluminum source are firstly added, the silicon source is added after the stirring is uniform, and finally the silanization reagent and the hydroxide are added, preferably, the silicon source is slowly added dropwise, and the purpose of slowly adding the silicon source dropwise is to further help the formation of the hierarchical pores.
The gel aging is carried out at room temperature, preferably for 24 h.
(2) Stirring and crystallizing;
specifically, crystallizing at 60-300 deg.C under stirring at 50-1000rpm for 1-15 days, and cooling to room temperature; preferably, crystallization is carried out at 100-200 ℃ under the stirring of 150-250rpm for 1-3 days.
(3) Washing, centrifuging and drying to obtain a ZSM-5 nano zeolite aggregate;
the obtained aggregate has particle size of 2-5 μm, ZSM-5 nanoparticles with size of 80-150nm, and mesoporous structure with pore diameter of 3-6nm due to stacking effect.
The invention is further described below by way of examples.
Example 1
The synthesis method comprises the following steps: adding 15g of water, 0.051g of aluminum sulfate octadecahydrate and 12g of tetrapropylammonium hydroxide into a reaction kettle, stirring uniformly, dropwise and slowly adding 5g of silica sol with the mass fraction of 40% in the stirring process, adding 4.0g of Dichlorodimethylsilane (DMCS), adding 1g of sodium hydroxide, stirring for 30min, and carrying out gel aging for 24h at room temperature. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product.
The XRD pattern of the product obtained in example 1 shows that the product has a characteristic diffraction peak of ZSM-5 and has higher crystallinity. The SEM photograph of the product obtained in example 1 shows that the sample is spherical, the particle size is 3 microns, the sample is formed by stacking nanoparticles, the aggregates have a mesoporous structure with the pore diameter of 3-6nm due to the stacking effect, and the particle size of the nano ZSM-5 is 100 nm. BET data for the product obtained in example 1 indicates that the sample has a micropore-mesopore distribution.
Example 2
After stirring uniformly under the same conditions as in example 1, 4g of silica powder was slowly added dropwise during the stirring, 4g of dichlorodimethylsilane was added, 1g of sodium hydroxide was added, the mixture was stirred for 30min, and the gel was aged at room temperature for 24 hours. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product. According to a sample XRD characterization result, a product can be seen to have a ZSM-5 characteristic diffraction peak, an SEM picture can show that the sample is spherical, the particle size is 4 micrometers, the sample is formed by stacking nanoparticles, the aggregate has a mesoporous structure with the pore diameter of 3-6nm due to the stacking effect, and the particle size of the nano ZSM-5 is 120 nm. BET data for the product obtained in example 2 indicates that the sample has a micropore-mesopore distribution.
Example 3
The synthesis method comprises the following steps: adding 15g of water, 0.016g of aluminum isopropoxide and 9g of tetrapropylammonium hydroxide into a reaction kettle, uniformly stirring, dropwise and slowly adding 5g of silica sol with the mass fraction of 40% in the stirring process, adding 5g of Trimethylchlorosilane (TMCS), adding sodium hydroxide, stirring for 30min, and carrying out gel aging for 24h at room temperature. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product. According to a sample XRD characterization result, a product can be seen to have a ZSM-5 characteristic diffraction peak, an SEM picture can show that the sample is spherical, the particle size is 2 micrometers, the sample is formed by stacking nanoparticles, the aggregate has a mesoporous structure with the pore diameter of 3-6nm due to the stacking effect, and the particle size of the nano ZSM-5 is 80 nm. BET data for the product obtained in example 3 indicate that the sample has a micropore-mesopore distribution.
Example 4
Using the same conditions as in example 4, 0.013g of sodium aluminate, 5g of Trimethylchlorosilane (TMCS) and 1g of sodium hydroxide were changed to an aluminum source to obtain a final product. According to the characterization result of the sample XRD, the product can be seen to have ZSM-5 characteristic diffraction peaks, the sample can be seen to be spherical in SEM pictures, the particle size is 2.5 microns and is formed by stacking nanoparticles, and the particle size of the nano ZSM-5 is 90 nm. BET data for the product obtained in example 4 indicate that the sample has a micropore-mesopore distribution.
Example 5
The synthesis method comprises the following steps: adding 15g of water, 0.051g of aluminum sulfate octadecahydrate, 12g of tetrapropylammonium bromide and 1.7g of sodium hydroxide solution with the mass fraction of 40% into a reaction kettle, stirring uniformly, dropwise and slowly adding 5g of silica sol with the mass fraction of 40% into the reaction kettle in the stirring process, adding 5g of Trimethylchlorosilane (TMCS), stirring for 30min, and carrying out gel aging for 24h at room temperature. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product. According to the characterization result of the sample XRD, the product can be seen to have ZSM-5 characteristic diffraction peaks, the sample can be seen to be spherical in SEM pictures, the particle size is 2 microns and is formed by stacking nanoparticles, and the particle size of the nano ZSM-5 is 100 nm. BET data for the product obtained in example 5 indicate that the sample has a micropore-mesopore distribution.
Example 6
After stirring uniformly under the same conditions as in example 6, 4g of silicon powder was slowly added dropwise during the stirring, a potassium hydroxide solution was added, 5g of Trimethylchlorosilane (TMCS) was added, stirring was carried out for 30min, and gel aging was carried out at room temperature for 24 hours. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product. According to the characterization result of the sample XRD, the product can be seen to have ZSM-5 characteristic diffraction peaks, the sample can be seen to be spherical in SEM pictures, the particle size is 3 microns and is formed by stacking nanoparticles, and the particle size of the nano ZSM-5 is 110 nm. BET data for the product obtained in example 6 indicates that the sample has a micropore-mesopore distribution.
Example 7
After stirring uniformly under the same conditions as in example 6, 2g of silica powder was slowly added dropwise during the stirring, a potassium hydroxide solution was added, 5g of dichlorodimethylsilane was added, the mixture was stirred for 30min, and the gel was aged at room temperature for 24 hours. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product. According to the characterization result of the sample XRD, the product can be seen to have ZSM-5 characteristic diffraction peaks, the sample can be seen to be spherical in SEM pictures, the particle size is 2 microns and is formed by stacking nanoparticles, and the particle size of the nano ZSM-5 is 110 nm. BET data for the product obtained in example 7 indicate that the sample has a micropore-mesopore distribution.
Example 8
The synthesis method comprises the following steps: adding 15g of water, 0.016g of aluminum isopropoxide, 2g of tetrapropylammonium bromide and 1.7g of sodium hydroxide solution with the mass fraction of 40% into a reaction kettle, stirring uniformly, dropwise and slowly adding 5g of silica sol with the mass fraction of 40% into the reaction kettle in the stirring process, adding 4.8g of dichlorodimethylsilane, stirring for 30min, and carrying out gel aging for 24h at room temperature. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product. According to the characterization result of the sample XRD, the product can be seen to have ZSM-5 characteristic diffraction peaks, the sample can be seen to be spherical in SEM pictures, the particle size is 5 microns and is formed by stacking nanoparticles, and the particle size of the nano ZSM-5 is 120 nm. BET data for the product obtained in example 8 indicates that the sample has a micropore-mesopore distribution.
Example 9
Using the same conditions as in example 8, 0.013g of sodium aluminate as the aluminum source was changed and 5g of dichlorodimethylsilane was added to obtain the final product. According to the characterization result of the sample XRD, the product can be seen to have ZSM-5 characteristic diffraction peaks, the sample can be seen to be spherical in SEM pictures, the particle size is 5 microns and is formed by stacking nanoparticles, and the particle size of the nano ZSM-5 is 110 nm. BET data for the product obtained in example 9 indicates that the sample has a micropore-mesopore distribution.
Example 10
Using the same conditions as in example 8, 0.013g of sodium aluminate was varied and 5g of Trimethylchlorosilane (TMCS) was added to give the final product. According to the characterization result of the sample XRD, the product can be seen to have ZSM-5 characteristic diffraction peaks, the sample can be seen to be spherical in SEM pictures, the particle size is 5 microns and is formed by stacking nanoparticles, and the particle size of the nano ZSM-5 is 110 nm. BET data for the product obtained in example 9 indicates that the sample has a micropore-mesopore distribution.
Comparative example 1
The synthesis method comprises the following steps: adding 15g of water, 0.051g of aluminum sulfate octadecahydrate and 12g of tetrapropylammonium hydroxide into a reaction kettle, adding no silanization reagent, stirring uniformly, dropwise and slowly adding 5g of silica sol with the mass fraction of 40% in the stirring process, adding sodium hydroxide, stirring for 30min, and carrying out gel aging for 24h at room temperature. Then crystallizing for 2 days at 180 ℃ under the stirring of 150rpm, cooling to room temperature, washing and centrifuging for 3 times by deionized water, and drying for 12 hours at 80 ℃ to obtain the final product. XRD characterization and SEM pictures showed that the resulting sample was ZSM-5 zeolite with cubic morphology, particle size 2-6um, and no aggregation.
Claims (7)
1. The preparation method of the nano ZSM-5 hierarchical pore aggregate comprises the following steps:
(1) water, T, Al source, Si source and R1And R2Adding the mixture into a reaction kettle, wherein the materials in a molar ratio are as follows: h2O/SiO2＝5-1000，T/SiO2＝0.1-200，Si/Al＝50-∞，R1/SiO2＝0.1-200，R2/SiO2Aging the gel for 0.01-10 hours; the T is a template agent, and the R is1Is a silylating agent, said R2Is a hydroxide;
(2) stirring and crystallizing;
(3) washing, centrifuging and drying to obtain a ZSM-5 nano zeolite aggregate;
the silanization reagent is at least one selected from dichlorodimethylsilane, trimethylchlorosilane and hexamethyldisilazane;
firstly adding water, a template agent and an aluminum source into a reaction kettle, then gradually and slowly adding a silicon source in a stirring process, and finally adding a silylation agent and hydroxide;
the silicon source is at least one selected from silica sol or amorphous silica powder.
2. The method as claimed in claim 1, wherein the stirring crystallization is carried out by crystallizing at 60-300 ℃ for 1-15 days under stirring at 50-1000rpm, and cooling to room temperature.
3. The method of claim 1, wherein the template agent is at least one selected from n-propylamine, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, and diethanolamine.
4. The method of claim 1, wherein the aluminum source is at least one selected from aluminum sulfate octadecahydrate, aluminum isopropoxide or metaaluminate, aluminate.
5. The method as set forth in claim 1, wherein the crystallization temperature is 100-2＝0.1-50, and the crystallization time is 1-3 days.
6. The method of claim 1, wherein the H is2O/SiO2＝5-500。
7. The method of claim 1, wherein the T/SiO is2＝0.1-50。
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| CN102001678A (en) * | 2010-10-30 | 2011-04-06 | 太原理工大学 | Middle hole ZSM-5 zeolite microsphere and preparation method thereof |
| CN102001681A (en) * | 2010-11-16 | 2011-04-06 | 浙江师范大学 | Method for synthesizing ZSM-5 zeolite |
| CN102583435A (en) * | 2012-03-20 | 2012-07-18 | 辽宁工业大学 | Preparation method of ZSM-5 zeolite molecular sieve with multi-stage ducts |
| CN104437602A (en) * | 2014-12-16 | 2015-03-25 | 湖南科技大学 | Multistage meso-porous ZSM-5 catalyst as well as preparation method and application method thereof |
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| CN102001678A (en) * | 2010-10-30 | 2011-04-06 | 太原理工大学 | Middle hole ZSM-5 zeolite microsphere and preparation method thereof |
| CN102001681A (en) * | 2010-11-16 | 2011-04-06 | 浙江师范大学 | Method for synthesizing ZSM-5 zeolite |
| CN102583435A (en) * | 2012-03-20 | 2012-07-18 | 辽宁工业大学 | Preparation method of ZSM-5 zeolite molecular sieve with multi-stage ducts |
| CN104437602A (en) * | 2014-12-16 | 2015-03-25 | 湖南科技大学 | Multistage meso-porous ZSM-5 catalyst as well as preparation method and application method thereof |
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