CN114477205B - Preparation method and application of MFI molecular sieve containing heteroatom Ti - Google Patents

Preparation method and application of MFI molecular sieve containing heteroatom Ti Download PDF

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CN114477205B
CN114477205B CN202210195678.4A CN202210195678A CN114477205B CN 114477205 B CN114477205 B CN 114477205B CN 202210195678 A CN202210195678 A CN 202210195678A CN 114477205 B CN114477205 B CN 114477205B
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CN114477205A (en
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赵毅罡
曾木
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Dalian Zhongcheng Weizhi Technology Development Co ltd
Dalian Jieer Catalytic Material Technology Co ltd
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    • 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
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention belongs to the technical field of zeolite molecular sieve materials, and provides a preparation method and application of an MFI molecular sieve containing heteroatom Ti. The preparation method comprises the following steps: uniformly dispersing a water-adsorbed full-silicon MFI molecular sieve with a mesoporous structure after roasting into an anhydrous alcohol solution of tetrabutyl titanate, and obtaining TiO after filtering, washing, drying and roasting 2 Uniformly dispersed all-silicon MFI molecular sieve with mesoporous structure is marked as Ti-S-1; and (3) placing the Ti-S-1 molecular sieve in an organic amine solution for crystallization reaction, filtering, washing, drying and roasting to obtain the MFI molecular sieve with the Ti-rich outer layer of the crystal. The preparation method provided by the invention has the advantages that the use amount of the organic template agent is low, the obtained molecular sieve material has mesopores, the outer layer of the crystal is rich in Ti, and when the molecular sieve material is used for preparing 1, 2-epoxyhexane by epoxidation of 1-hexene, the accessible active centers are more, and the diffusion resistance of the reactant molecular sieve is small, so that the catalyst has good catalytic activity and catalytic selectivity.

Description

Preparation method and application of MFI molecular sieve containing heteroatom Ti
Technical Field
The invention belongs to the field of zeolite molecular sieve material preparation, and relates to a preparation method and application of an MFI molecular sieve containing heteroatom Ti.
Background
Zeolite molecular sieves having an MFI topology belong to the Pentasil type and include ZSM-5 molecular sieves, TS-1 molecular sieves and all-silica-1 molecular sieves. The zeolite molecular sieve has a special ten-membered ring channel structure and proper acidity, is widely applied to the fields of petrochemical industry, coal chemical industry, fine chemical industry and environmental protection, and is an important industrial catalyst.
Among them, the TS-1 molecular sieve containing heteroatom titanium (Ti) has unique oxidation-reduction capability due to the existence of isolated titanium species in four-coordination form on the molecular sieve framework, and is an effective catalyst for epoxidation reaction. In a series of catalytic epoxidation reactions, such as alkane epoxidation, alkene epoxidation, phenol hydroxylation, ketone ammoximation, etc., TS-1 molecular sieves all exhibit good catalytic activity. However, the application of the TS-1 molecular sieve is limited by the small pore diameter (0.55 nm) of the internal pore canal of the molecular sieve, which is unfavorable for the diffusion of reactants and products of the macromolecular sieve: on the one hand, macromolecular reactants are difficult to access to the active center; on the other hand, the reaction product is difficult to diffuse, and macromolecular products are easily polymerized to cause deactivation of active center carbon deposition. At present, two main methods for solving the problem are available, one is to introduce a mesoporous structure into a microporous structure of a TS-1 molecular sieve to form a transmission channel which is favorable for the diffusion of macromolecular compounds; another approach is to synthesize ultrafine molecular sieves with nanoscale dimensions. The material with the TS-1 mesoporous composite structure can improve the diffusion performance of the product, make up the defects of a microporous molecular sieve, provide a favorable space configuration for macromolecular reaction, but lead to non-framework Ti generation and activity loss in the treatment process. The crystal granularity of the molecular sieve is reduced from micron level to nanometer level, and the performances of mass transfer, adsorption, catalysis and the like are changed. Compared with the TS-1 molecular sieve, the nano TS-1 molecular sieve has larger outer surface area and higher intra-crystal diffusion rate, has short pore channels and a large number of inter-crystal pores, has more excellent performances in the aspects of improving the utilization rate of the catalyst, enhancing the macromolecular conversion capability, reducing the deep reaction, improving the selectivity and the like, and has better activity, selectivity and strong carbon deposit deactivation resistance in some hydrocarbon catalytic conversion reactions. However, the molecular sieve crystal terminals are usually terminated by silicon hydroxyl groups, and the catalytic reaction active centers (Ti) are mostly distributed in the pore channels of the crystal framework, so that the number of the molecular sieve crystal terminals is small on the outer surface of the crystal, and the molecular sieve is far from enough for macromolecular reaction.
1, 2-epoxyhexane is an important precursor for fine chemical engineering and is widely used for synthesizing medicines, textiles, pesticides and surfactants. At present, the direct synthesis method of oxygen, peroxide and peroxy acid is industrially adopted, but the synthesis method can generate a large amount of byproducts and waste materials, and has serious environmental problems and certain potential safety hazard. Therefore, development of an environment-friendly epoxidation process is urgently required. Therefore, in recent years, the TS-1 molecular sieve is used for catalyzing the epoxidation of 1-hexene to prepare 1, 2-epoxyhexane, and the method has the characteristics of few byproducts, high selectivity, mild reaction conditions, environmental friendliness and the like, and is attracting attention. However, because of the large 1-hexene molecules, diffusion in the sieve pores of TS-1 molecules is limited, so that the catalyst is fast in deactivation, short in single-pass reaction period and difficult to regenerate, and the industrialization progress of the catalyst is hindered. Therefore, the preparation of an MFI molecular sieve with a mesoporous structure and rich Ti on the outer surface is an important way to solve the problems.
Disclosure of Invention
The invention provides a preparation method and application of an MFI molecular sieve containing heteroatom Ti. The method is different from the existing method in that: tiO is prepared by a sol-gel method 2 Dispersing on the inner and outer surfaces of the all-silicon MFI molecular sieve with a mesoporous structure; and then placing the mixture in an organic amine solution for crystallization to obtain the MFI molecular sieve with the Ti-rich crystal outer layer. The method has the advantages that the use amount of the organic template agent is low, the obtained molecular sieve material has mesopores, the outer layer of the crystal is rich in Ti, the molecular sieve material can be close to an active center when used for preparing 1, 2-epoxyhexane by epoxidation of 1-hexene, and the diffusion resistance of the reactant molecular sieve is small.
The specific technical scheme of the invention is as follows: a preparation method of an MFI molecular sieve containing heteroatom Ti comprises the following steps:
s1, uniformly dispersing a water-adsorbed full-silicon MFI molecular sieve with a mesoporous structure after roasting into an anhydrous alcohol solution of tetrabutyl titanate, and obtaining TiO after filtering, washing, drying and roasting 2 Uniformly dispersed all-silicon MFI molecular sieve with mesoporous structure is marked as Ti-S-1;
s2, placing the Ti-S-1 molecular sieve into an organic amine solution for crystallization reaction, filtering, washing, drying and roasting the solid to obtain the MFI molecular sieve with the Ti-rich outer layer of the crystal.
The alcohol in S1 is one or more of methanol, ethanol, isopropanol and butanol.
The dosage of the tetrabutyl titanate in the S1 is as follows: siO (SiO) 2 With TiO 2 In a molar ratio of 33 to 200, wherein tetrabutyl titanate is present as TiO 2 Meter, siO 2 Is derived from an all-silicon MFI molecular sieve with a mesoporous structure.
The organic amine in S2 is one or more of TPAOH, TEAOH, TMAOH, n-butylamine and ethylenediamine; the mass concentration of the organic amine solution is 0.1% -2.5%.
The amount of the organic amine in S2 is as follows: organic amine and SiO 2 The mol ratio of (2) is 0.01-0.9, siO 2 Is derived from an all-silicon MFI molecular sieve with a mesoporous structure.
The crystallization temperature in S2 is 25-200 ℃; the crystallization time is 1 to 100 hours, and further, the crystallization reaction is performed in a stirring state, and the stirring can be continuous or intermittent.
The all-silicon MFI molecular sieve with the mesoporous structure is prepared by placing the all-silicon MFI molecular sieve in an alkali solution with the concentration of 0.001-0.3mol/L, reacting with stirring, filtering, washing, drying and roasting the solid after the reaction is finished, wherein the liquid-solid ratio is 1-100.
The alkali is one or more of sodium hydroxide, potassium hydroxide, ammonia water, urea and sodium bicarbonate.
The reaction temperature is 25-100 ℃; the reaction time is 0.5-80 hours. The stirring may be continuous or intermittent.
The preparation method of the all-silicon MFI molecular sieve comprises the following steps:
s1 preparation of gel by template-free system
Mixing silicon source and alkali source uniformly to obtain initial gel, adding seed crystal into the initial gel under stirring state to obtain synthetic gel, wherein Na is contained in the initial gel 2 O：H 2 O：SiO 2 The material mole ratio of (2) is 0.02-0.25: 10 to 50:1, wherein the silicon source is SiO 2 Calculated by the alkali source of Na 2 A meter of O; the mass of the added seed crystal is SiO in the initial gel 2 0 to 20 weight percent of the mass;
s2 gel crystallization
And (3) carrying out crystallization reaction on the prepared synthetic gel, and filtering, washing, drying and roasting the solid to obtain the all-silicon MFI molecular sieve.
The silicon source is one or more of tetraethoxysilane, silica sol, white carbon black and solid silica gel; the alkali source is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
The crystallization temperature of the synthetic gel is 80-200 ℃; the crystallization time is 1-80 hours. Crystallization may be performed under static conditions, but stirring is recommended for uniform particle size of the crystallized product. The stirring is preferably carried out to achieve uniform mixing, and the stirring can be continuous or intermittent.
The beneficial effects of the invention are as follows: the sol-gel method is adopted to pre-adsorb water into the mesopores of the all-silicon MFI molecular sieve with a mesoporous structure, and the water required by the hydrolysis reaction of the titanium ester is provided by slowly releasing the adsorbed water through the molecular sieve pore channels, so that the generation of TiO (titanium oxide) at an excessively fast hydrolysis rate can be inhibited 2 Agglomerated particles, and the wide distribution of water molecules in the pore canal of the molecular sieve, and controllable titanium ester hydrolysis to obtain high-dispersion TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Finally, the obtained TiO with high dispersion on the inner and outer surfaces 2 Is crystallized by the MFI molecular sieve with mesoporous structure, so that TiO 2 And (3) entering a molecular sieve framework to obtain the MFI molecular sieve with the Ti-rich crystal outer layer. The MFI molecular sieve with the mesoporous structure and rich Ti on the outer layer of the crystal is favorable for the diffusion of reactant products, and the active center Ti is mainly distributed in the outer layer of the crystal and the mesopores, so that the accessibility is high and the reactant conversion is favorable. In addition, the invention reduces the usage amount of the organic template agent.
Detailed Description
Comparative example 1
TS-1 (USP 4410501) was synthesized by classical method, 250ml deionized water was added to 84g of ethyl orthosilicate and 14.7g of tetrapropylammonium hydroxide, and stirred for 20 minutes to obtain a raw material silicon solution; tetrabutyl titanate and isopropanol are mixed according to the mass ratio of 1:0.6, and the mixture is stirred for 15 minutes to obtain a raw material titanium solution; 15.7ml of the prepared raw material titanium solution is added into the raw material silicon solution, and stirred for 30 minutes to obtain uniform gel; transferring the gel into a stainless steel reaction kettle, and crystallizing for 120 hours under autogenous pressure at 170 ℃; filtering, washing to neutrality, drying at 110deg.C, and calcining at 540 deg.C for 6 hr to obtain classical TS-1 molecular sieve (named TS-1).
Comparative example 2
After-modification of TS-1 samples, the catalytic activity is improved, and the treatment process is as follows: TS-1 is placed in a hydrothermal synthesis kettle with polytetrafluoroethylene, tetrapropylammonium hydroxide treatment solution with a certain concentration is added, the mixture is treated for 36 hours under the autogenous pressure of 180 ℃, filtered, washed to be neutral, dried at 110 ℃ and baked at 540 ℃ for 6 hours, and the modified TS-1 molecular sieve (marked as TS 1-P) is obtained.
Example 1
The first step:
200g of ethyl orthosilicate and 50g of water are uniformly mixed under vigorous stirring, 15g of NaOH is added to uniformly mix to obtain initial gel, and then 1.68g of seed crystal is added to prepare uniform synthetic gel. The initial gel mixture had the following molar composition: na (Na) 2 O/SiO 2 ＝0.2，H 2 O/SiO 2 =11.5, where the silicon source is in SiO 2 Calculated by the alkali source of Na 2 A meter of O; the mass of the added seed crystal is SiO in the initial gel 2 Mass = 3wt%. The resultant synthetic gel was put into an autoclave lined with polytetrafluoroethylene, crystallized at 170℃for about 24 hours under continuous stirring, cooled to room temperature after the completion of the reaction, filtered, washed, dried (drying temperature 110 ℃ C., drying time 12 hours), and calcined (calcining temperature 540 ℃ C., calcining time 4 hours). The relative crystallinity of the all-silica MFI zeolite was 90% and the particle size was a highly aggregated nano zeolite (designated S-1) as measured by X-ray powder diffraction.
And a second step of:
10g S-1 powder was added to 30g of 0.01mol/L sodium hydroxide solution under vigorous stirring, reacted at room temperature for 30min, filtered, washed, dried (drying temperature 110 ℃ C., drying time 12 h), and calcined (calcining temperature 540 ℃ C., calcining time 4 h). The relative crystallinity of the all-silica MFI zeolite having a mesoporous structure therein was 88% as measured by X-ray powder diffraction method, and the particle size was a highly aggregated nano zeolite (designated as M-S-1).
And a third step of:
under vigorous stirring, 10g M-S-1 is adsorbed and saturated by 8g of deionized water, then added into a mixed solution of 1g of tetrabutyl titanate and 5g of ethanol, reacted for 1h, filtered, washed, dried (drying temperature 110 ℃ C., drying time 12 h) and roasted (roasting temperature 540 ℃ C., roasting time 4 h), and then Ti-S-1 is obtained. 10g of solid powder Ti-S-1 was added to 50g of TPAOH solution (2.5% by weight) with stirring, mixed and put into an autoclave lined with polytetrafluoroethylene, crystallized at 170℃for about 48 hours with continuous stirring, cooled to room temperature after the reaction was completed, filtered, washed, dried (drying temperature 110 ℃ C., drying time 12 hours), and calcined (calcining temperature 540 ℃ C., calcining time 4 hours). The MFI molecular sieve in which Ti is rich in the outer layer of the crystal has a relative crystallinity of 90% and the particle size is a highly aggregated nano zeolite (designated as Ti-M-S-1) as measured by X-ray powder diffraction method.
Example 2
Example 1 was repeated, replacing the ethyl orthosilicate in the first step of example 1 with a silica sol. The relative crystallinity of the all-silica MFI zeolite was 92% and the particle size was a highly aggregated nano zeolite as measured by X-ray powder diffraction. The final crystalline outer layer Ti-rich MFI molecular sieve has a relative crystallinity of 89% and a particle size of highly aggregated nano zeolite (designated as Ti-M-S-1-1).
Example 3
Example 1 was repeated, replacing the sodium hydroxide in the first step of example 1 with ammonia. The relative crystallinity of the all-silica MFI zeolite was 85% and the particle size was a highly aggregated nano zeolite as measured by X-ray powder diffraction. The final crystalline outer layer of the Ti-rich MFI molecular sieve had a relative crystallinity of 85% and a particle size of highly aggregated nano zeolite (designated as Ti-M-S-1-2).
Example 4
Example 1 was repeated, replacing the sodium hydroxide in the second step of example 1 with urea. The final crystalline outer layer Ti-rich MFI molecular sieve has a relative crystallinity of 90% and a particle size of highly aggregated nano zeolite (designated as Ti-M-S-1-3).
Example 5
Example 1 was repeated, changing the concentration of TPAOH in the third step of example 1 to 1.8wt%. The final crystalline outer layer of Ti-rich MFI molecular sieve has a relative crystallinity of 92% and a particle size of highly aggregated nano zeolite (designated as Ti-M-S-1-4).
Example 6
Example 1 was repeated, changing the amount of TPAOH used in the third step of example 1 to 80g. The final crystalline outer layer of Ti-rich MFI molecular sieve had a relative crystallinity of 94% and a particle size of highly aggregated nano zeolite (designated Ti-M-S-1-5).
Example 7
XRF and XPS tests were performed on the above comparative examples 1-2 and examples 1-6, and the results are shown in table 1, which illustrate that titanium of the MFI molecular sieve containing heteroatom Ti obtained by the present method is mainly distributed in the outer layer of the crystal, and the macromolecular reactant (hexene) is easily accessible to the reactive center to participate in the reaction.
Table 1 titanium distribution of example samples
Si/Ti TS-1 TS-1-P Ti-M-S-1 Ti-M-S-1-1 Ti-M-S-1-2 Ti-M-S-1-3 Ti-M-S-1-4 Ti-M-S-1-5
XRF 36.4 37.1 40 42 40 41 40 40
XPS 37.0 36.8 20 18 19 18.5 19.8 19.2

Claims (9)

1. A preparation method of an MFI molecular sieve containing heteroatom Ti is characterized in that: the method comprises the following steps:
s1, uniformly dispersing a water-adsorbed full-silicon MFI molecular sieve with a mesoporous structure after roasting into an anhydrous alcohol solution of tetrabutyl titanate, and obtaining TiO after filtering, washing, drying and roasting 2 Uniformly dispersed all-silicon MFI molecular sieve with mesoporous structure is marked as Ti-S-1;
s2, placing the Ti-S-1 molecular sieve into an organic amine solution for crystallization reaction, filtering, washing, drying and roasting the solid to obtain the MFI molecular sieve with the Ti-rich outer layer of the crystal.
2. The method as claimed in claim 1The preparation method of the MFI molecular sieve containing the heteroatom Ti is characterized by comprising the following steps: the dosage of the tetrabutyl titanate in the S1 is as follows: siO (SiO) 2 With TiO 2 The molar ratio of (2) is 33-200.
3. The method for preparing the MFI molecular sieve containing the heteroatom Ti as set forth in claim 1, wherein: the organic amine in S2 is one or more of TPAOH, TEAOH, TMAOH, n-butylamine and ethylenediamine; the mass concentration of the organic amine solution is 0.1% -2.5%.
4. The method for preparing the MFI molecular sieve containing the heteroatom Ti as set forth in claim 1, wherein: the amount of the organic amine in S2 is as follows: organic amine and SiO 2 The molar ratio of (2) is 0.01-0.9.
5. The method for preparing the MFI molecular sieve containing the heteroatom Ti as set forth in claim 1, wherein: the crystallization temperature in the step S2 is 25-200 ℃; the crystallization time is 1-100 hours.
6. The method for preparing the MFI molecular sieve containing the heteroatom Ti as set forth in claim 1, wherein: in S2, the crystallization reaction is carried out under stirring.
7. The method for preparing the MFI molecular sieve containing the heteroatom Ti as set forth in claim 1, wherein: the preparation method of the all-silicon MFI molecular sieve with the mesoporous structure comprises the following steps: placing the all-silicon MFI molecular sieve into an alkali solution with the concentration of 0.001-0.3mol/L, wherein the liquid-solid ratio is 1-100, stirring for reaction, and filtering, washing, drying and roasting the solid after the reaction is finished to obtain the all-silicon MFI molecular sieve with a mesoporous structure.
8. The method for preparing the MFI molecular sieve containing the heteroatom Ti as set forth in claim 7, wherein: the preparation method of the all-silicon MFI molecular sieve comprises the following steps:
s1 preparation of gel by template-free system
Mixing silicon source and alkali source uniformly to obtain initial gel, adding seed crystal under stirring state to obtain uniform synthetic gel, wherein Na is contained in the initial gel 2 O：H 2 O：SiO 2 The material molar ratio of (1) is 0.02-0.25: 10-50: 1, a step of; the mass of the added seed crystal is SiO in the initial gel 2 0-20wt% of the weight of the catalyst;
s2 gel crystallization
And (3) carrying out crystallization reaction on the prepared synthetic gel, and filtering, washing, drying and roasting the solid to obtain the all-silicon MFI molecular sieve.
9. The method for preparing the MFI molecular sieve containing the heteroatom Ti as set forth in claim 8, wherein: the crystallization temperature of the synthetic gel in the step S2 is 80-200 ℃ and the crystallization time is 1-80 hours; the crystallization reaction is performed in a stirred state.
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