CN111825104A - Preparation of High Silica Y Molecular Sieve by Seed Crystal Method - Google Patents

Abstract

The present application discloses a preparation method of a high-silicon Y molecular sieve, and a high-silicon Y molecular sieve prepared by the method, belonging to the field of catalyst preparation. The method includes: a) mixing raw materials containing aluminum source, silicon source, alkali metal source, nitrogen-containing heterocyclic template R and water to obtain an initial gel; b) mixing a silica-alumina molecular sieve with FAU or EMT structure The seed crystals are added to the initial gel obtained in step a) and stirred to obtain a synthetic gel; c) the synthetic gel obtained in step b) is crystallized. The anhydrous chemical composition of the high-silicon _Y molecular sieve _is kM·mR·(Six Aly)O ₂ , and the silicon-aluminum oxide ratio thereof is 7-30. The method according to the present application can synthesize Y molecular sieves with high silicon-to-aluminum ratio while avoiding post-processing processes with complicated processes, high energy consumption and heavy pollution, and the synthesized molecular sieves have good hydrothermal/thermal stability, and can be applied to fluidization Catalytic Cracking (FCC), with good catalytic activity.

Description

Preparation of High Silica Y Molecular Sieve by Seed Crystal Method

technical field

The present application relates to a method for preparing a high-silicon Y molecular sieve, and more particularly, to a method for synthesizing high-silica by introducing a nitrogen-containing heterocyclic template into a synthetic gel system and adding a silicon-aluminum molecular sieve crystal having an FAU or EMT structure. The method for Y molecular sieve and the high silicon Y molecular sieve with FAU structure obtained by the method belong to the field of catalyst preparation.

Background technique

Y molecular sieve is a silica-alumina molecular sieve with FAU topology, which is mainly used in fluid catalytic cracking (FCC) and is currently the most widely used molecular sieve material. The framework Si-Al ratio of Y molecular sieve plays a decisive role in its catalytic performance. The higher the Si-Al ratio, the better the catalytic activity and stability. At present, the high-silicon Y molecular sieves used in industry are mainly obtained by chemical/physical methods such as dealumination. This post-processing method is cumbersome, energy-intensive, and polluting. Direct hydrothermal synthesis can effectively avoid the above-mentioned problems. shortcomings while maintaining the integrity of the crystal structure and the uniformity of aluminum distribution. Therefore, it is very important to explore the direct synthesis of high silica-alumina ratio Y molecular sieves for the catalytic cracking process.

For the direct synthesis of high-silicon Y molecular sieves, it was initially synthesized in a non-template system, that is, no organic template was added to the reaction gel, and only by adjusting the gel ratio and adjusting the crystallization time, seeds or inorganic guides The preparation method of the agent is used to achieve the purpose of improving the silicon-aluminum ratio of the Y molecular sieve, but the effect is very small, and the silicon-aluminum ratio is difficult to reach 6.

The use of organic structure directing agents brought the synthesis of Y molecular sieves into a new field. In 1987, US Patent No. 4,714,601 disclosed a FAU homogeneous polymorph named ECR-4 with a silicon-to-aluminum ratio greater than 6. It is obtained by hydrothermal crystallization at 70-120 DEG C in the presence of crystal seed by using alkyl or hydroxyalkyl quaternary ammonium salt as template agent.

In 1990, U.S. Patent No. 4,931,267 disclosed a FAU homogeneous polymorph named ECR-32 with a silicon-aluminum ratio greater than 6, which was based on tetrapropyl and/or tetrabutylammonium It is obtained by hydrothermal crystallization at 120°C and has high thermal stability.

In 1990, French Delprato et al. (Zeolites, 1990, 10(6): 546-552) used crown ethers as templates to synthesize FAU molecular sieves with cubic structure for the first time. However, the expensive and highly toxic crown ethers limit its industrial application. After that, US Pat. No. 5,385,717 used polyethylene oxide as a template to synthesize a Y molecular sieve with a silicon-alumina ratio greater than 6.

SUMMARY OF THE INVENTION

According to one aspect of the present application, there is provided a method for preparing a high-silicon Y molecular sieve, which is prepared by adding a silica-alumina molecular sieve crystal seed to a synthetic gel system and introducing a nitrogen-containing heterocyclic template into the synthetic gel system. Promote the synthesis of high-silicon (silicon-aluminum oxide ratio of 7 to 30) Y molecular sieves.

The preparation method of the high-silicon Y molecular sieve is characterized in that, comprises the following steps:

a) mixing raw materials containing aluminum source, silicon source, alkali metal source, nitrogen-containing heterocyclic template R and water to obtain an initial gel;

b) adding the silica-alumina molecular sieve crystal seeds with FAU or EMT structure to the initial gel obtained in step a) and stirring to obtain a synthetic gel;

c) Crystallizing the synthetic gel obtained in step b) to obtain the high-silicon Y molecular sieve.

Optionally, the silicon source is selected from at least one of methyl orthosilicate, ethyl orthosilicate, silica sol, solid silica gel, silica and sodium silicate.

Optionally, the aluminum source is selected from at least one of sodium metaaluminate, aluminum oxide, aluminum hydroxide, aluminum isopropoxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate, and aluminum nitrate.

Optionally, the alkali metal source is selected from at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide.

Optionally, the nitrogen-containing heterocyclic template R is selected from at least one of nitrogen-containing heterocyclic compounds and derivatives thereof.

Preferably, the nitrogen-containing heterocyclic template R is selected from pyridine, N-methylpyridine, N-ethylpyridine, N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine Pyridine, 1-ethyl-2-propylpyridine hydroxide, piperidine, N,N-dimethylpiperidine, N,N-dimethyl-3,5-diethylpiperidine hydroxide, hydroxide N,N-Dimethyl-3,5-dipropylpiperidine, N,N-diethyl-3,5-dipropylpiperidine Hydroxide, N,N-Diethyl-2, Hydroxide Hydroxide 6-Dimethylpiperidine, N,N-Dimethyl-2,6-diethylpiperidine Hydroxide, Imidazole, 1-Ethyl-3-butylimidazole Hydroxide, 1-Ethyl Hydroxide- 3-butyl-4-propylimidazole, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-benzyl-3-butylimidazole hydroxide, Of piperazine, N-methylpiperazine, 1,4-dipropylpiperazine, 1-methyl-4-ethylpiperazine, 1-ethyl-4-butyl-5-methylpiperazine at least one.

Optionally, in step a), the aluminum source, silicon source, alkali metal source, nitrogen-containing heterocyclic template R and water are mixed according to the following molar ratio:

1Al ₂ O ₃ :(10～200)SiO ₂ :(0～30)M ₂ O:(1～45)R:(50～6000)H ₂ O;

Among them, the mole number of silicon source is in SiO ₂ ; the mole number of aluminum source is in Al ₂ O ₃ ; the mole number of nitrogen-containing heterocyclic template R is in the mole number of R itself; the mole number of alkali metal source is in Its corresponding alkali metal M corresponds to the number of moles of metal oxide M ₂ O.

Preferably, in step a), the aluminum source, silicon source, alkali metal source, nitrogen-containing heterocyclic template R and water are mixed according to the following molar ratio:

1Al ₂ O ₃ :(10～200)SiO ₂ :(0.1～25)M ₂ O:(1～45)R:(50～6000)H ₂ O;

Among them, the mole number of silicon source is in SiO ₂ ; the mole number of aluminum source is in Al ₂ O ₃ ; the mole number of nitrogen-containing heterocyclic template R is in the mole number of R itself; the mole number of alkali metal source is in Its corresponding alkali metal M corresponds to the number of moles of metal oxide M ₂ O.

Optionally, the silicon-alumina-oxide ratio of the silicon-alumina molecular sieve seeds having the FAU or EMT structure is greater than or equal to 2.

Optionally, the silicon-alumina-oxide ratio of the silicon-alumina molecular sieve seed crystal having the FAU or EMT structure is 2.5-200.

Preferably, the upper limit of the silicon-alumina oxide ratio of the silicon-alumina molecular sieve seed crystal with FAU or EMT structure is selected from 200, 180, 150, 120, 100, 80, 50, 20, 10, 6, 5, and the lower limit is selected from From 2, 2.5, 3, 5, 10, 20.

Optionally, the silica-alumina molecular sieve seed crystal having the FAU or EMT structure is selected from at least one of Na-type, _NH4 -type and H-type zeolite molecular sieves.

Optionally, in step b), the added amount of the silica-alumina molecular sieve crystal seeds with FAU or EMT structure is 5-30 wt% of the mass of the silicon source in the initial gel calculated as SiO ₂ .

Optionally, in step b), the added amount (mass) of the seed crystals accounts for 5-20% of the SiO ₂ content in the initial gel.

Preferably, in step b), the upper limit of the amount of the silica-alumina molecular sieve seed crystals with FAU or EMT structure added relative to the mass percentage of the silicon source in the initial gel in terms of SiO ₂ is selected from 30wt%, 29wt% %, 28wt%, 27wt%, 26wt%, 25wt%, 24wt%, 23wt%, 22wt%, 21wt%, 20wt%, 19wt%, 18wt%, 17wt%, 16wt%, 15wt%, 14wt%, 13wt%, 12wt%, 11wt%, 10wt%, 9wt%, 8wt%, 7wt%, 6wt%, the lower limit is selected from 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt% , 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%.

Optionally, in step b), the stirring is performed for 1 to 48 hours.

Preferably, in step b), the upper limit of the stirring time is selected from 48 hours, 44 hours, 40 hours, 36 hours, 32 hours, 28 hours, 24 hours, 20 hours, 16 hours, 12 hours, 8 hours, 4 hours, 2 hours, the lower limit is selected from 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours, 44 hours.

In one embodiment, in step b), the silica-alumina molecular sieve crystals having the FAU or EMT structure are added to the initial gel and stirred for 1-4 hours to obtain the synthetic gel.

Optionally, in step c), the crystallization is performed at 90-180° C. for 0.1-15 days.

Preferably, in step c), the upper limit of the crystallization temperature is selected from 180°C, 170°C, 160°C, 150°C, 140°C, 135°C, 130°C, 125°C, 120°C, 115°C, 110°C , 105°C, 100°C, 95°C, the lower limit is selected from 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 145°C, 160°C.

Preferably, in step c), the upper limit of the crystallization time is selected from 15 days, 14 days, 13 days, 12 days, 11 days, 10 days, 8 days, 6 days, 4 days, 2 days, 1 day, 0.5 days, 0.3 days, the lower limit is selected from 0.1 days, 0.2 days, 0.3 days, 0.5 days, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days , 11 days, 12 days, 13 days, 14 days.

Optionally, in step c), the crystallization is performed under autogenous pressure.

In the method, the crystallization mode in step c) may be dynamic crystallization or static crystallization, and may also be a combination of the two crystallization modes.

Optionally, in step c), the crystallization is performed in a dynamic or static manner.

Optionally, in step c), the crystallization is performed in a dynamic and static manner, for example, in a static manner and then a dynamic manner.

In this application, dynamic crystallization means that the slurry in the crystallization kettle is in a non-stationary state, and static crystallization means that the slurry in the crystallization kettle is in a stationary state.

Optionally, in step c), after the crystallization, the solid product is filtered, washed and dried to obtain the high silicon Y molecular sieve.

In the method, washing, filtering, separating and drying the obtained Y molecular sieve are all conventional operations, wherein the drying can be performed by placing at 100-110° C. for 12 hours.

In a specific embodiment, the synthesis process of the high-silicon Y molecular sieve is as follows:

a1) Preparation of synthetic gel: aluminum source, silicon source, alkali metal source (M), nitrogen-containing heterocyclic template R and deionized water according to 1Al ₂ O ₃ : (10～200) SiO ₂ : (0.1～25 ) M ₂ O: (1～45) R: (50～6000) mole ratio of H ₂ O at room temperature by mixing and stirring to obtain the initial gel, then adding a certain amount of seed crystals and stirring for 1～48 hours to obtain the synthetic gel;

b1) Synthesis of high-silicon Y molecular sieve: the above-mentioned synthetic gel is crystallized under autogenous pressure at 90-180°C for 0.2-15 days, after the crystallization is completed, the solid product is filtered and separated, washed with deionized water until neutral, and dried. Obtain high silica Y molecular sieve.

According to another aspect of the present application, there is provided a high-silicon Y molecular sieve prepared by the method, the molecular sieve has a silicon-alumina oxide ratio as high as 7-30, good hydrothermal/thermal stability, and can be used for fluidized catalytic cracking (FCC) ) with good catalytic activity.

The anhydrous chemical composition of described high silicon Y molecular sieve is as shown in formula I:

_kM ·mR·( _SixAly )O ₂ formula I

Wherein, M is selected from at least one in alkali metal element sodium, potassium, cesium;

R represents nitrogen-containing heterocyclic template agent;

k represents the number of moles of alkali metal elements corresponding to each mole of ( _SixAly )O ₂ , k ₌ 0～0.2;

m represents the number of moles of nitrogen-containing heterocyclic template R corresponding to each mole of ( _SixAly )O ₂ , m ₌ 0.01-0.2;

x and y represent the mole fractions of Si and Al, respectively, 2x/y=7-30, and x+y=1.

Optionally, M is Na and/or K, preferably Na.

Optionally, k=0.01-0.15; m=0.03-0.15.

Preferably, k=0.02～0.13; m=0.04～0.12.

Optionally, under the condition of x+y=1, the upper limit of 2x/y is selected from 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16 , 15, 14, 13, 12, 11, 10, 9 or 8, the lower limit is selected from 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 or 29.

According to yet another aspect of the present application, a catalyst is provided, and the high-silicon Y molecular sieve with FAU topology prepared according to the method described in the present application can be used for fluidized catalytic cracking catalysts and bifunctional catalysis such as hydrocracking, hydrogenation Supports and catalysts for reactions such as desulfurization.

In the context of this application, the term "silicon-aluminum ratio" means the molar ratio of silicon to aluminum in molecular sieves, calculated as _SiO2 and _Al2O3 , which is in contrast to the " _2x /y" and "2x/y" described in this application. "Silicon aluminum oxide ratio" has the same meaning.

The beneficial effects that this application can produce include but are not limited to:

1) The preparation method of the high-silicon Y molecular sieve provided by the present application, which is to synthesize a Y molecular sieve with a silicon-aluminum ratio up to 7-30 by introducing a nitrogen-containing heterocyclic template agent into a synthetic gel and adding a silicon-aluminum molecular sieve crystal seed, And the synthesized product has high crystallinity and purity, good hydrothermal/thermal stability, can be applied to fluid catalytic cracking (FCC), and has good catalytic reaction activity.

2) The preparation method of the high-silicon Y molecular sieve provided by the present application can avoid the post-processing process with complicated process, high energy consumption and heavy pollution, and has great significance in the field of actual chemical production.

Description of drawings

FIG. 1 is an X-ray diffraction (XRD) spectrum of sample X1.

FIG. 2 is a scanning electron microscope (SEM) photograph of sample X1.

FIG. 3 is a silicon nuclear magnetic resonance ( ²⁹ Si-NMR) spectrum of sample X1.

FIG. 4 is an X-ray diffraction (XRD) spectrum of the comparative sample V1.

Detailed ways

As mentioned above, the present application relates to a high-silicon Y molecular sieve with FAU topology and a method for synthesizing the same. The anhydrous chemical composition of the molecular sieve is _kM ·mR·( _SixAly ) _O2 , wherein M is a base Metal, k represents the number of moles of alkali metal ions M corresponding to each mole of ( _{Six Aly} )O ₂ , R represents the nitrogen-containing heterocyclic template, and m represents the number of moles of the template R corresponding to each mole of ( _Six A _y )O ₂ The number of moles, the ratio of silicon to aluminum oxide (2x/y) is 7-30; the method is to synthesize high-silicon Y molecular sieve by introducing nitrogen-containing heterocyclic template into the synthetic gel system and adding seed crystals.

The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials and reagents in the examples of this application are purchased through commercial channels.

The analytical method in the embodiment of the present application is as follows:

X-ray powder diffraction phase analysis (XRD) used X'Pert PRO X-ray diffractometer from PANalytical, the Netherlands, Cu target, Kα radiation source (λ=0.15418nm), voltage 40kV, current 40mA.

Scanning electron microscope (SEM) test was performed using a Hitachi SU8020 field emission scanning electron microscope with an accelerating voltage of 2kV.

The elemental composition was determined using a Magix 2424 X-ray fluorescence analyzer (XRF) from Philips.

Silicon nuclear magnetic ( ²⁹ Si-NMR) experiments were carried out on a Bruker Avance III 600 (14.1 Tesla) spectrometer with a 7mm dual-resonance probe, a rotational speed of 6 kHz, a high-power proton decoupling program, a sampling number of 1024, and a π/4 pulse width. is 2.5 μs, the sampling delay is 10 s, and the chemical shift reference is 4,4-dimethyl-4-propanesulfonate (DSS), corrected to 0 ppm.

Carbon nuclear magnetic resonance ( ¹³ C MAS NMR) experiments were carried out on a Bruker Avance III 600 (14.1 Tesla) spectrometer with a 4 mm triple-resonance probe at a rotational speed of 12 kHz, with amantadine as the chemical shift reference, calibrated to 0 ppm.

Example 1: Preparation of sample X1

Preparation of synthetic gel: 0.7 g of sodium aluminate (Al ₂ O ₃ : 48.3 wt %, Na ₂ O: 36.3 wt %, China Pharmaceutical (Group) Shanghai Chemical Reagent Co., Ltd.), 0.20 g of sodium hydroxide, 13.74 g of hydroxide N,N-dimethyl-3,5-dipropylpiperidine (25wt%) was dissolved in 1.82g deionized water and stirred until clear, and 13.3g of silica sol (SiO ₂ : 30wt%, Shenyang Chemical Co., Ltd. was added dropwise) company) and stirred for 2 hours, then added 0.4 g of Y zeolite with a silicon-alumina oxide ratio of 3 as a seed crystal, and continued stirring for 2 hours.

Synthesis of high-silicon Y molecular sieve: transfer the above-mentioned synthetic gel into a stainless steel reaction kettle, rotate and crystallize at 130 °C for 5d under autogenous pressure, after crystallization, separate solid-liquid and wash to neutrality, and dry at 100 °C for 12h , denoted as sample X1.

The X-ray powder diffraction pattern (XRD) of the sample X1 is shown in FIG. 1 , which indicates that the sample is a molecular sieve with a FAU framework structure. The scanning electron microscope (SEM) of the sample X1 is shown in FIG. 2 , which shows that the particles of the sample are small flakes with a size of 50 nm to 200 nm. The ²⁹ Si MAS NMR spectrum of sample X1 is shown in Figure 3. The framework silicon-aluminum ratio calculated by fitting is consistent with that calculated by XRF. According to the normalization of XRF and ¹³ C MAS NMR analysis, the elemental composition of sample X1 is obtained: 0.07Na·0.07R ¹ ·(Si _0.86 Al _0.14 )O ₂ , wherein R ¹ is N,N-dimethyl-3,5-dipropylpiperidine hydroxide.

Example 2: Preparation of samples X2 to X30

The rubber compounding process of samples X2-X30 is the same as that of Example 1. The raw material types, molar ratio, seed crystal addition amount (represented by the mass ratio of seed crystal mass to _SiO2 in the initial gel), crystallization conditions, product structure and The silicon-aluminum ratio (the product silicon-aluminum ratio was determined by X-ray fluorescence analyzer (XRF)) and the sample composition are shown in Table 1.

Among them, in the preparation of samples X1~X20, the ratio of silicon to aluminum oxide was 3, 2.8, 3.5, 40, 5, 6, 6, 6, 6, 7, 92, 10, 3.5, 4, 6, 8, 4, 35, Silica-alumina molecular sieves with FAU structure of 12 and 20 were used as seeds, and the molecular sieve seeds were purchased from Zibo Runxin Chemical Technology Co., Ltd. In the preparation of samples X21~X30, silicon-alumina molecular sieves with EMT structure with a silicon-alumina oxide ratio of 7, 7, 8.5, 7, 8, 10, 21, 32, 8 and 7 were used as seeds, and the molecular sieve seeds were obtained from Henan. Huanyu Molecular Sieve Co., Ltd. purchased.

Comparative Example 1: Preparation of Comparative Samples V1 to V30

The specific batching process is the same as the preparation of sample X1 in Example 1, the difference is that there is no seed crystal addition step. See Table 2 for details of the raw material types, molar ratio, crystallization conditions and product structures for synthesizing each product. The obtained samples were recorded as comparative samples V1 to V30.

Example 3: Characterization analysis of samples X1-X30 and comparative samples V1-V30

The phases of samples X1-X30 and comparative samples V1-V30 were analyzed by X-ray diffraction method.

The results show that the samples X1 to X30 prepared in Examples 1 and 2 are all Y molecular sieves with high purity and high crystallinity. The typical representative is the XRD pattern of the sample X1 in Figure 1, and the SEM photo of the sample X1 in Figure 2. Figure 3 is the silicon NMR spectrum of sample X1. The XRD patterns of samples X2-X30 are close to those in Figure 1, that is, the position and shape of the diffraction peaks are basically the same, and the relative peak intensity fluctuates within a range of ±5% depending on the synthesis conditions, indicating that samples X1-X30 have the structural characteristics of Y molecular sieves And no impurity crystals, and its silicon-alumina ratio is much higher than conventional Y zeolite. It can be seen that in the synthesis of the high silicon Y molecular sieve according to the present application, the introduction of a nitrogen-containing heterocyclic template is the key to the synthesis of the high silicon Y molecular sieve according to the present application.

In Table 2, the comparative samples V1 to V30 are all amorphous, and the typical representative is the XRD spectrum of the comparative sample V1 as shown in FIG. 4 . It can be seen that in the synthesis of the high silicon Y molecular sieve according to the present application, in addition to the introduction of the nitrogen-containing heterocyclic template, the addition of seed crystals is also necessary.

The above are only a few embodiments of the present application, and are not intended to limit the present application in any form. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Without departing from the scope of the technical solution of the present application, any changes or modifications made by using the technical content disclosed above are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims (8)

1. A preparation method of a high-silicon Y molecular sieve is characterized by comprising the following steps:

a) mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, a nitrogen-containing heterocyclic template agent R and water to obtain initial gel;

b) adding a silicon-aluminum molecular sieve seed crystal with an FAU or EMT structure into the initial gel obtained in the step a), and stirring to obtain a synthetic gel;

c) crystallizing the synthesized gel obtained in the step b) to obtain the high-silicon Y molecular sieve.

2. The method according to claim 1, wherein the silicon source is selected from at least one of methyl orthosilicate, ethyl orthosilicate, silica sol, solid silica gel, white carbon black and sodium silicate;

the aluminum source is at least one selected from sodium metaaluminate, aluminum oxide, aluminum hydroxide, aluminum isopropoxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate and aluminum nitrate;

the alkali metal source is selected from at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide.

3. The method according to claim 1, wherein the nitrogen-containing heterocyclic template agent R is selected from at least one of nitrogen-containing heterocyclic compounds and derivatives thereof;

preferably, the nitrogen-containing heterocyclic template R is selected from pyridine, N-methylpyridine, N-ethylpyridine, N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine, 1-ethyl-2-propylpyridine hydroxide, piperidine, N-dimethylpiperidine, N-dimethyl-3, 5-diethylpiperidine hydroxide, N-dimethyl-3, 5-dipropylpiperidine hydroxide, N-diethyl-2, 6-dimethylpiperidine hydroxide, N-dimethyl-2, 6-diethylpiperidine hydroxide, imidazole, 1-ethyl-3-butylimidazole hydroxide, N-propylpyridine, N-butylpyridinium hydroxide, N-dimethyl-3, 5-diethylpiperidine hydroxide, N-diethyl-2, 6-dimethylpiperidine hydroxide, N-dimethyl-2, 1-ethyl-3-butyl-4-propylimidazole hydroxide, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-benzyl-3-butylimidazole hydroxide, piperazine, N-methylpiperazine, 1, 4-dipropylpiperazine, 1-methyl-4-ethylpiperazine, and 1-ethyl-4-butyl-5-methylpiperazine.

4. The method of claim 1, wherein in step a), the aluminum source, the silicon source, the alkali metal source, the nitrogen-containing heterocyclic templating agent R, and the water are mixed in the following molar ratios:

1Al₂O₃:(10～200)SiO₂:(0～30)M₂O:(1～45)R:(50～6000)H₂O；

preferably, in step a), the aluminum source, the silicon source, the alkali metal source, the nitrogen-containing heterocyclic templating agent R and water are mixed in the following molar ratios:

1Al₂O₃:(10～200)SiO₂:(0.1～25)M₂O:(1～45)R:(50～6000)H₂O；

wherein the mole number of the silicon source is SiO₂Counting; the mole number of the aluminum source is Al₂O₃Counting; the mole number of the nitrogen-containing heterocyclic template agent R is calculated by the mole number of R per se; the molar number of the alkali metal source is equal to the metal oxide M corresponding to the corresponding alkali metal M₂And the mole number of O.

5. The method of claim 1, wherein the silicoaluminophosphate molecular sieve seed crystal having the FAU or EMT structure has a silica alumina ratio of 2 or more;

preferably, the silicon-aluminum oxide ratio of the silicon-aluminum molecular sieve seed crystal with the FAU or EMT structure is 2.5-200;

preferably, the seeds of the silicoaluminophosphate molecular sieve with FAU or EMT structure are selected from Na type, NH type₄At least one of type and H zeolite molecular sieves;

preferably, in step b), the amount of the silicon source of the silicon-aluminum molecular sieve seeds with FAU or EMT structure added in the initial gel is SiO₂5-30 wt% of the mass;

preferably, in the step b), the stirring is performed for 1 to 48 hours.

6. The method according to claim 1, wherein in step c), the crystallization is performed at 90 to 180 ℃ for 0.1 to 15 days;

preferably, in step c), the crystallization is carried out in a dynamic or static manner;

preferably, in step c), the crystallization is carried out in a combination of dynamic and static.

7. The method of any one of claims 1 to 6, wherein the high silicon Y molecular sieve has an anhydrous chemical composition as shown in formula I:

kM·mR·(Si_xAl_y)O₂formula I

Wherein M is at least one of alkali metal elements of sodium, potassium and cesium;

r represents a nitrogen-containing heterocyclic template;

k represents (Si) per mole_xAl_y)O₂The molar number of the corresponding alkali metal element, k is 0.0-0.2;

m represents (Si) per mole_xAl_y)O₂The mole number of the corresponding nitrogen-containing heterocyclic template agent R, wherein m is 0.01-0.2;

x and y represent the mole fractions of Si and Al, 2x/y is 7-30, and x + y is 1.

8. The method according to claim 7, wherein M is Na and/or K;

preferably, k is 0.01 to 0.15; m is 0.03-0.15;

more preferably, k is 0.02 to 0.13; m is 0.04 to 0.12.

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