CN115594192B - NaY zeolite with high silicon-aluminum ratio and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of NaY zeolite materials and discloses a high silicon-to-aluminum ratio NaY zeolite and its preparation method and application. The preparation method is: uniformly disperse silicon source A, aluminum source A and sodium salt in aqueous solution A, and then After oxidation, the directing agent A is obtained; the directing agent A, the silicon source B, the aluminum source B and the alkali source A are evenly dispersed in the aqueous solution B. After aging, crystallization is carried out at 85 to 100°C to obtain zeolite gel seed crystals. ; Evenly disperse silicon source C and aluminum source C in aqueous solution C, and after aging, obtain directing agent B; uniformly disperse directing agent B, silicon source D, zeolite gel seed crystal, alkali source B and aluminum source D in In aqueous solution D, after aging, crystallization is performed at 85 to 100°C to obtain the high silicon to aluminum ratio NaY zeolite. The preparation method of the present invention is simple, green and environmentally friendly, has a short preparation cycle, and the prepared high silicon to aluminum ratio NaY zeolite has a crystallinity of more than 90% and a silicon to aluminum ratio of 5.5 to 7.0, and is suitable for industrial production.

Description

A high silicon to aluminum ratio NaY zeolite and its preparation method and application

Technical field

The present invention relates to the technical field of NaY zeolite materials, and in particular to a high silicon to aluminum ratio NaY zeolite and its preparation method and application.

Background technique

Y zeolite is widely used in petroleum refining and other fields because of its advantages such as developed three-dimensional pores, adjustable acidity, and good thermal and hydrothermal stability. Crystallinity and silicon-to-aluminum ratio (SiO ₂ /Al ₂ O ₃ ) are one of the most important factors affecting the properties and functions of Y zeolite. Higher crystallinity means that Y zeolite has higher stability and more active centers. A higher silicon-to-aluminum ratio not only means that Y zeolite has higher stability, but also means that Y zeolite has low acid density. , many strong acid centers, high catalytic cracking activity, good coke selection and other advantages.

NaY zeolite is the main raw material for the production of ultra-stable Y zeolite (USY molecular sieve), SiCl ₄ gas phase ultra-stable Y zeolite, and mesoporous Y zeolite. Its properties directly affect the performance of the above-mentioned materials produced, and then affect the performance of the catalyst.

At present, the directing agent method is mainly used to prepare NaY zeolite in the prior art. However, the crystallinity of the NaY zeolite prepared by this method is about 83%, and its silicon-aluminum (SiO ₂ /Al ₂ O ₃ ) molar ratio is low. 5.0 or so, the NaY zeolite prepared by this method cannot withstand the complex and harsh conditions of the post-modification process. The crystallinity loss is large during the treatment process, making it difficult to meet the requirements for high-performance catalyst production.

In order to solve the above technical problems, those skilled in the art try to improve the silica-aluminum ratio and crystallinity of NaY zeolite, and those skilled in the art have proposed two types of synthesis methods of high-silica-aluminum ratio NaY zeolite, the template-free method and the template method. Among them, the template-free method adds metal cesium ions to the reactant gel to synthesize a high silica-aluminum ratio Y zeolite with a silica-aluminum ratio between 5.0-7.0. However, this method requires multiple ion exchanges and roasting. method to remove cesium ions. Compared with the template-free method, the high silica-aluminum ratio NaY zeolite synthesized using the template agent is easier to undergo ion exchange during subsequent modification. Therefore, the template method is widely used to synthesize high-silica-aluminum ratio NaY zeolite. Research. The template method is further divided into organic template method and organic template method. The organic template method is used to synthesize NaY zeolite, with a silicon-to-aluminum ratio as high as 6.0-18.2. The selection of organic template agents mainly focuses on organic ammoniums and crown ethers. The addition of organic templates often prolongs the crystallization time of high silicon to aluminum ratio NaY zeolite, and some even require crystallization for more than ten days or a month. Moreover, the secondary utilization of organic templates is still a problem. The current treatment method is generally to remove the organic templates through roasting, which will cause environmental pollution, increase energy consumption and production costs. Therefore, the organic template-free method for synthesizing high-silica-to-aluminum ratio NaY zeolite has been favored by the industry. For example, CN101767799A discloses a synthesis method of NaY zeolite with a high silicon-aluminum ratio. This method chooses to stir at a relatively low temperature (0-10°C) for 24 hours to synthesize a directing agent, and at a lower temperature (15-80°C) ℃) to crystallize the reactant gel, and synthesized NaY zeolite with a silicon-to-aluminum ratio of 6.0 or more. However, due to the poor dispersion of the directing agent in the gel, the crystallinity of the sample is less than 90%, and the synthesis temperature of the directing agent is low, making it unsuitable for industrial applications.

To this end, the present invention proposes a high silicon to aluminum ratio NaY zeolite and its preparation method and application.

Contents of the invention

In order to solve the above deficiencies in the prior art, the present invention provides a high silicon to aluminum ratio NaY zeolite and its preparation method and application. The synthesis method of the present invention has a short crystallization time, is easy to operate, and does not need to change existing production equipment, and The prepared NaY zeolite has high crystallinity and silicon-to-aluminum ratio.

A kind of high silicon to aluminum ratio NaY zeolite of the present invention and its preparation method and application are realized through the following technical solutions:

The first object of the present invention is to provide a preparation method of high silicon to aluminum ratio NaY zeolite, which includes the following steps:

Step 1, prepare zeolite gel seed crystal

According to the molar ratio of (5.0×10 ^-2 -20) sodium salt: (8-20) Na ₂ O: Al ₂ O ₃ : (10-20) SiO ₂ : (100-350) H ₂ O, the silicon source A. Aluminum source A and sodium salt are evenly dispersed in aqueous solution A. After the first aging treatment, directing agent A is obtained;

Subsequently, according to the molar ratio of (2-4)Na ₂ O: Al ₂ O ₃ : (6-15) SiO ₂ : (100-300) H ₂ O, the directing agent A, silicon source B, aluminum source B and Alkali source A is evenly dispersed in aqueous solution B. After the second aging treatment, the first crystallization treatment is performed at 85-100°C to obtain zeolite gel seed crystals;

Step 2, crystallization to form high silicon to aluminum ratio NaY zeolite

According to the molar ratio of (10-20)Na ₂ O: Al ₂ O ₃ : (10-20) SiO ₂ : (100-350) H ₂ O, the silicon source C and the aluminum source C are evenly dispersed in the aqueous solution C, After the third aging treatment, the guiding agent B is obtained;

Subsequently, according to the molar ratio of (2-4)Na ₂ O: Al ₂ O ₃ : (7-12) SiO ₂ : (100-300) H ₂ O, the directing agent B, the silicon source D, and the zeolite gel crystal are The seed, alkali source B and aluminum source D are evenly dispersed in the aqueous solution D. After the fourth aging treatment, the second crystallization treatment is performed at 85 to 100°C to obtain the high silicon to aluminum ratio NaY zeolite.

Further, the silicon source A and silicon source B are selected from one or both of water glass and alkaline silica sol.

Further, both the aluminum source A and the aluminum source B are selected from one or both of sodium metaaluminate and overbased sodium metaaluminate.

Further, the sodium salt is one or more of NaCl, NaBr and NaI.

Further, the silicon source C and the silicon source D are both selected from one or more of silica sol, water glass, white carbon black and silica gel.

Further, the aluminum source C and the aluminum source D are each selected from one or more of sodium metaaluminate, over-based sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide.

Further, the dosage of the sodium salt accounts for 3 wt% to 18 wt% of the guiding agent A.

Further, the usage amount of the zeolite gel seed crystal accounts for 1 wt% to 20 wt% of the directing agent B.

Further, the temperature of the first aging treatment is 20-35°C, and the aging time is 12-24 hours.

Further, the temperature of the second aging treatment is 30-60°C, and the aging time is 1-12 hours.

Further, the time of the first crystallization treatment is 6 to 60 hours.

Further, the temperature of the third aging treatment is 20-35°C, and the aging time is 12-24 hours.

Further, the temperature of the fourth aging treatment is 30-65°C, and the aging time is 1-12 hours.

Further, the time of the second crystallization treatment is 12 to 60 hours.

The second object of the present invention is to provide a high silicon to aluminum ratio NaY zeolite prepared by the above preparation method.

Further, the crystallinity of the high silicon to aluminum ratio NaY zeolite is ≥90%, and the silicon to aluminum ratio is 5.5-7.0.

The third object of the present invention is to provide an application of the above-mentioned high silicon to aluminum ratio NaY zeolite in the preparation of adsorbents and catalysts.

Compared with the prior art, the present invention has the following beneficial effects:

In the present invention, the directing agent A prepared from sodium salt, silicon source A, aluminum source A and water is first used as the directing agent for the zeolite gel seed crystal, and is reacted with the silicon source B, the aluminum source B and the alkali source A to form a zeolite gel seed containing The zeolite gel seed crystal is rich in high silicon crystal nucleus precursor, and then the obtained zeolite gel seed crystal is used as a precursor material to regulate the polymerization reaction of silicon and aluminum substances during the crystal growth process. Among them, the zeolite gel seed crystal contains rich The high-silicon crystal nucleation precursor not only provides abundant crystal nuclei for the zeolite crystallization process, thereby shortening the crystallization time; it also has the function of regulating the gel silicon-alumina environment and promoting the entry of silicon into the zeolite framework, making the silicon-aluminum ratio in the zeolite framework High, which can ultimately improve the properties of high silicon to aluminum ratio NaY zeolite.

The preparation method of the present invention does not require the addition of any organic templates or organic additives, has a simple process, is green and environmentally friendly, and can achieve rapid preparation, and the preparation method of the present invention can be prepared in existing industrial production equipment without adding other equipment. Suitable for industrial production.

The high silicon to aluminum ratio NaY zeolite prepared by the method of the present invention has a crystallinity of more than 90%, a silicon to aluminum ratio of 5.5-7.0, and has thermal stability and acidity advantages, which is of great significance for improving the performance of the catalytic cracking catalyst.

Description of the drawings

Figure 1 is an XRD pattern of high silicon to aluminum ratio NaY zeolite in Example 1 of the present invention;

Figure 2 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite in Example 2 of the present invention;

Figure 3 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite in Example 3 of the present invention;

Figure 4 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite in Example 4 of the present invention;

Figure 5 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite in Example 5 of the present invention;

Figure 6 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite in Example 6 of the present invention;

Figure 7 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite of Comparative Example 1 of the present invention;

Figure 8 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite of Comparative Example 2 of the present invention;

Figure 9 is an XRD pattern of the high silicon to aluminum ratio NaY zeolite of Comparative Example 3 of the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

The invention provides a high silicon to aluminum ratio NaY zeolite, and its preparation method includes the following steps:

Step 1, prepare zeolite gel seed crystal

1.1 Preparation of guiding agent A

Evenly disperse silicon source A, aluminum source A and sodium salt in aqueous solution A, and obtain directing agent A after the first aging treatment;

It should be noted that the present invention does not limit the specific types of silicon source A, aluminum source A and sodium salt, as long as the mixture of silicon source A, aluminum source A, sodium salt and aqueous solution A can be made, the sodium salt, Na ₂ O , Al ₂ O ₃ , SiO ₂ and H ₂ O molar ratio is (5.0×10 ^-2 -20) sodium salt: (8-20) Na ₂ O: Al ₂ O ₃ : (10-20) SiO ₂ : (100-350) H ₂ O is sufficient, where Na ₂ O is derived from silicon source A and aluminum source A, Al ₂ O ₃ is derived from aluminum source A, and SiO ₂ is derived from silicon source A. And in the present invention, the silicon source A is selected from one or both of water glass and alkaline silica sol; the aluminum source A is selected from one or both of sodium metaaluminate and high-alkali sodium metaaluminate; sodium The salt is any one of NaCl, NaBr and NaI.

The present invention does not limit the specific process parameters of the first aging treatment, as long as the silicon source A, the aluminum source A and the sodium salt can be fully contacted with the aqueous solution A to form the directing agent A with uniform components. Optionally, the present invention Aging at a temperature of 20 to 35°C for 12 to 24 hours. In order to make the silicon source A, aluminum source A and sodium salt more fully contact with the aqueous solution A, mechanical stirring is used for mixing. The present invention does not specifically limit the specific process parameters of stirring, which are determined according to the actual situation, as long as the materials are Just stir it up, the time is usually 1 to 2 hours.

1.2 Formation of zeolite gel seeds

Directing agent A, silicon source B, aluminum source B and alkali source A are uniformly dispersed in aqueous solution B. After the second aging treatment, the first crystallization treatment is performed at 85-100°C to obtain zeolite gel. seed crystal;

It should be noted that the present invention does not limit the specific types of silicon source B, aluminum source B and alkali source A, as long as the directing agent A can be mixed with silicon source B, aluminum source B, alkali source A and aqueous solution B to form a mixture, The molar ratio of Na ₂ O, Al ₂ O ₃ , SiO ₂ and H ₂ O is (2-4)Na ₂ O: Al ₂ O ₃ : (6-15) SiO ₂ : (100-300) H ₂ O, that is Yes, the silicon source B is selected from one or both of water glass and alkaline silica sol; the aluminum source B is selected from one or both of sodium metaaluminate and high-alkali sodium metaaluminate, and When sodium metaaluminate and/or overbased sodium metaaluminate is used as aluminum source B, since sodium metaaluminate and overbased sodium metaaluminate are highly alkaline and also exist as alkali source A, there is no need to add an additional alkali source. ; The amount of sodium salt accounts for 3wt% to 18wt% of the guiding agent A.

The present invention does not limit the specific process parameters of the second aging treatment, as long as the directing agent A and the silicon source B, the aluminum source B, the alkali source A and the aqueous solution B can be fully contacted to form a zeolite gel seed crystal precursor with uniform components. That is, optionally, the present invention is aged at a temperature of 30 to 60°C for 1 to 12 hours. In order to make the directing agent A and the silicon source B, the aluminum source B and the alkali source A and the aqueous solution B more fully contact, mechanical stirring is used for mixing. The present invention does not specifically limit the specific process parameters of stirring. According to the actual situation To confirm, just stir the materials, usually for 1 to 2 hours.

The present invention does not limit the specific process parameters of the first crystallization treatment, as long as the zeolite gel seed solid material is prepared. Optionally, the present invention performs the crystallization treatment at a temperature of 85 to 100° C. for 6 to 60 hours.

Step 2, crystallization to form high silicon to aluminum ratio NaY zeolite

2.1 Preparation of guiding agent B

The silicon source C and the aluminum source C are evenly dispersed in the aqueous solution C, and after the third aging treatment, the directing agent B is obtained;

It should be noted that the present invention does not limit the specific types of silicon source C and aluminum source C, as long as the mixture of silicon source C, aluminum source C and aqueous solution C can be made, Na ₂ O, Al ₂ O ₃ , SiO ₂ and The molar ratio of H ₂ O is (10-20)Na ₂ O: Al ₂ O ₃ : (10-20) SiO ₂ : (100-350) H ₂ O, where the silicon source C is selected from silica sol, One or more of water glass, white carbon black and silica gel; aluminum source C is selected from one or more of sodium metaaluminate, high-alkali sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide.

The present invention does not limit the specific process parameters of the third aging treatment, as long as the silicon source C and aluminum source C can be fully contacted with the aqueous solution C to form a uniform directing agent B. Optionally, the present invention is based on the 20th to 35th steps. Aging at ℃ for 12 to 24 hours. In order to make the silicon source C and aluminum source C more fully contact with the aqueous solution C, mechanical stirring is used for mixing. The present invention does not specifically limit the specific process parameters of stirring, which are determined according to the actual situation, as long as the materials are stirred. Yes, the time is generally 1 to 2 hours.

2.2 Formation of high silicon to aluminum ratio NaY zeolite

Directing agent B, silicon source D, zeolite gel seed crystal, alkali source B and aluminum source D are evenly dispersed in aqueous solution D. After the fourth aging treatment, the second crystallization is performed at 85-100°C. After treatment, NaY zeolite with high silicon to aluminum ratio is obtained;

It should be noted that the present invention does not limit the specific types of silicon source D, zeolite gel seed crystal, alkali source B and aluminum source D, as long as the directing agent B can be combined with silicon source D, zeolite gel seed crystal, alkali source B In the mixture of aluminum source D and aqueous solution C, the molar ratio of Na ₂ O, Al ₂ O ₃ , SiO ₂ and H ₂ O is (2-4)Na ₂ O: Al ₂ O ₃ : (7-12) SiO ₂ : (100-300)H ₂ O is enough, where the silicon source D is selected from one or more of silica sol, water glass, white carbon black and silica gel; the aluminum source D is selected from sodium metaaluminate, One or more of high-based sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide, and when sodium metaaluminate and/or high-based sodium metaaluminate is used as the aluminum source D, due to sodium metaaluminate It has strong alkalinity with high-alkali sodium metaaluminate and also exists as alkali source B, so the reaction can be achieved without adding an additional alkali source; and the amount of zeolite gel seed crystal accounts for 1wt% to 20wt% of the directing agent B. .

The present invention does not limit the specific process parameters of the second crystallization treatment, as long as a high silicon to aluminum ratio NaY zeolite solid material is prepared. Optionally, the present invention performs the crystallization treatment at a temperature of 85 to 100°C for 12 to 60 hours.

Example 1

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and its preparation method is as follows:

S1, Preparation of zeolite gel seed crystals:

S1.1 Preparation of guiding agent A

Take 30.08g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.50g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%), 10.40g NaCl and 8.56g deionized water are mixed evenly, stirred for 1 hour at 35°C at a stirring rate of 150 r/min, and then left to stand for 12 hours to obtain the guiding agent A; wherein, water glass is used It is silicon source A, high-based sodium metaaluminate is used as aluminum source A, and NaCl is used as sodium salt A.

S1.2 Obtain NaY zeolite gel seed crystal

Take 118.32g water glass (SiO ₂ content is 27.6wt%, Na _2O content is 8.96wt%), put it into a beaker, and place it in a 60°C water bath. Under stirring conditions, add the above-mentioned directing agent A and 23.90g high alkali. Sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 24g deionized water, stir at a stirring speed of 150r/min for 30 minutes, then add 79.20g aluminum sulfate (Al ₂ O ₃ content is 7.6wt%) continue to stir at a stirring rate of 150r/min for 30 minutes to mix evenly, and then let it stand for aging for 1 hour to prepare a reaction mixture gel; put the above reaction mixture gel into the reaction kettle and put it in the reaction kettle. Crystallize in an oven at 90°C for 6 hours, then filter, wash and dry to obtain NaY zeolite gel seed crystals, in which water glass is used as silicon source B, high-alkali sodium metaaluminate and aluminum sulfate are used as aluminum source B, and at the same time Water glass and high-alkali sodium metaaluminate together serve as alkali source A.

Preparation of S2, high silicon to aluminum ratio NaY zeolite

S2.1 Preparation of guiding agent B

Take 18.85g of water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), and add 20.80g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%) and 6.56g of water were mixed evenly, stirred evenly at 25°C, and aged for 24 hours to prepare the directing agent B; wherein, water glass was used as the silicon source C, and high-alkali sodium metaaluminate was used as the aluminum source C.

S2.2 obtains high silicon to aluminum ratio NaY zeolite

Take 104.32g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), put it into a beaker, and place it in a 60°C water bath. Under stirring conditions, add the above-mentioned directing agent B and 5g of step (1 ), 18.15g of high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 24g water, stir for 30 minutes and then add 59.83 g of aluminum sulfate (Al ₂ O ₃ content is 7.6 wt%), stir and mix evenly, and age for 12 hours to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle, crystallize at 90°C for 24 hours, and then filter , washing and drying to obtain high silicon-aluminum ratio NaY zeolite, in which water glass is used as the silicon source D, high-alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source D, and at the same time, water glass and high-alkali sodium metaaluminate are used as a base. Source B.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this example are shown in Figure 1;

The relative crystallinity of the sample prepared in this example is 93%, and the silicon-aluminum (SiO ₂ /Al ₂ O ₃ ) molar ratio is 6.65.

Example 2

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and its preparation method is as follows:

S1, Preparation of zeolite gel seed crystals:

S1.1 Preparation of guiding agent A

Take 20.88g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.50g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%), 1.70g NaBr and 8.56g water were mixed evenly, stirred evenly at 25°C, and aged for 24h to prepare the directing agent A; among them, water glass was used as the silicon source A, and high-alkali sodium metaaluminate was used as the silicon source A. Aluminum source A uses NaBr as sodium salt A.

S1.2 Obtain NaY zeolite gel seed crystal

Take 118.18g water glass (SiO ₂ content is 27.6wt%, Na _2O content is 8.96wt%), put it into a beaker, and place it in a 30°C water bath. Under stirring conditions, add the above-mentioned directing agent A and 5.90g high alkali. Sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 37.02g deionized water, stir for 30 minutes and then add 49.20g aluminum sulfate (Al ₂ O ₃ content is 7.6wt %) stir and mix evenly, and age for 12 hours to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 100°C for 24 hours, then filter, wash and dry to obtain NaY zeolite gel seed crystals, where , water glass is used as the silicon source B, high-alkali sodium metaaluminate and aluminum sulfate are used together as the aluminum source B, and at the same time, water glass and high-alkali sodium metaaluminate are also present together as the alkali source A.

Preparation of S2, high silicon to aluminum ratio NaY zeolite

S2.1 Preparation of guiding agent B

Take 16.80g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 18.65g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%) and 8.86g deionized water, stir evenly at 20°C, and age for 12 hours to prepare the guiding agent B; among them, water glass is used as the silicon source C, and high-alkali sodium metaaluminate is used as the aluminum source. C.

S2.2 obtains high silicon to aluminum ratio NaY zeolite

Take 114.32g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), put it into a beaker, and place it in a 30°C water bath. Under stirring conditions, add the above-mentioned directing agent B and 3g of step (1 ), 13.44g of overbased sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 18.51g deionized water, after stirring for 30 minutes Then add 29.33g aluminum sulfate (Al ₂ O ₃ content is 7.6wt%), stir and mix evenly, and age for 1 hour to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 90°C for 12 hours. , then filtered, washed and dried to obtain high silicon-aluminum ratio NaY zeolite, in which water glass is used as the silicon source D, high-alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source D, and water glass and high-alkali sodium metaaluminate are used at the same time Together as an alkali source B.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this example are shown in Figure 2;

The relative crystallinity of the sample prepared in this example is 92%, and the molar ratio of silicon to aluminum (SiO ₂ /Al ₂ O ₃ ) is 5.96.

Example 3

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and its preparation method is as follows:

S1, Preparation of zeolite gel seed crystals:

S1.1 Preparation of guiding agent A

Take 20.88g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.50g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%), 8.50g NaI and 8.56g deionized water were mixed evenly, stirred evenly at 20°C, and aged for 16 hours to prepare the directing agent A; among them, water glass was used as the silicon source A, and high-alkali metaaluminic acid was used Sodium is aluminum source A, and NaI is sodium salt A.

S1.2 Obtain NaY zeolite gel seed crystal

Take 108.18g of water glass (SiO ₂ content is 27.6wt%, Na _2O content is 8.96wt%), put it into a beaker, and place it in a 50°C water bath. Under stirring conditions, add the above-mentioned directing agent A and 10.90g high alkali. Sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 27.02g deionized water, stir for 30 minutes and then add 54.48g aluminum sulfate (Al ₂ O ₃ content is 7.6wt %) Stir and mix evenly, and age for 1 hour to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 96°C for 40 hours, then filter, wash and dry to obtain NaY zeolite gel seed crystals. In the embodiment, water glass is used as the silicon source B, over-based sodium metaaluminate and aluminum sulfate are used together as the aluminum source B, and at the same time, water glass and high-based sodium metaaluminate are used together as the alkali source A.

Preparation of S2, high silicon to aluminum ratio NaY zeolite

S2.1 Preparation of guiding agent B

Take 20.80g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.65g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%) and 8.36g of deionized water, stir evenly at 35°C, and age for 18 hours to prepare the guiding agent B; among them, water glass is used as the silicon source C, and high-alkali sodium metaaluminate is used as the aluminum source. C.

S2.2 obtains high silicon to aluminum ratio NaY zeolite

Take 110.32g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), put it into a beaker, and place it in a 50°C water bath. Under stirring conditions, add the above-mentioned directing agent B and 5g of step (1 ), 10.44g of overbased sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 20.51g deionized water, after stirring for 30 minutes Then add 49.33g aluminum sulfate (Al ₂ O ₃ content is 7.6wt%), stir and mix evenly, and age for 3 hours to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 100°C for 15 hours. , then filtered, washed and dried to obtain high silicon-aluminum ratio NaY zeolite, in which water glass is used as the silicon source D, high-alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source D, and water glass and high-alkali sodium metaaluminate are used at the same time Together as an alkali source B.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this example are shown in Figure 3;

The relative crystallinity of the sample prepared in this example is 94%, and the silicon-aluminum (SiO ₂ /Al ₂ O ₃ ) molar ratio is 6.03.

Example 4

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and its preparation method is as follows:

S1, Preparation of zeolite gel seed crystals:

S1.1 Preparation of guiding agent A

Take 30.08g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.50g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%), 5.20g NaCl and 8.56g deionized water were mixed evenly, stirred evenly at 25°C, and aged for 20h to prepare the guiding agent A; among them, water glass was used as the silicon source A, and high-alkali metaaluminic acid was used Sodium is aluminum source A, and NaCl is used as sodium salt A.

S1.2 Obtain NaY zeolite gel seed crystal

Take 118.32g water glass (SiO ₂ content is 27.6wt%, Na _2O content is 8.96wt%), put it into a beaker, and place it in a 50°C water bath. Under stirring conditions, add the above-mentioned directing agent A and 23.90g high alkali. Sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 24g deionized water, stir for 30 minutes and then add 79.20g aluminum sulfate (Al ₂ O ₃ content is 7.6wt% ) Stir and mix evenly, and age for 6 hours to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 98°C for 30 hours, then filter, wash and dry to obtain NaY zeolite gel seed crystals, wherein, Water glass is used as the silicon source B, high-alkali sodium metaaluminate and aluminum sulfate are used together as the aluminum source B, and at the same time, water glass and high-alkali sodium metaaluminate are used together as the alkali source A.

Preparation of S2, high silicon to aluminum ratio NaY zeolite

S2.1 Preparation of guiding agent B

Take 18.85g of water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), and add 20.80g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%) and 6.56g of deionized water, stir evenly at 32°C, and age for 18 hours to prepare the guiding agent B; among them, water glass is used as the silicon source C, and high-alkali sodium metaaluminate is used as the aluminum source. C.

S2.2 obtains high silicon to aluminum ratio NaY zeolite

Take 104.32g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), put it into a beaker, and place it in a 50°C water bath. Under stirring conditions, add the above-mentioned directing agent B and 5g of step (1 ), 18.15g of high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 24g deionized water, stir for 30 minutes and then Add 59.83g aluminum sulfate (Al ₂ O ₃ content is 7.6wt%), stir and mix evenly, and age for 6 hours to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 98°C for 24 hours. Then filter, wash and dry to obtain high silicon to aluminum ratio NaY zeolite, in which water glass is used as the silicon source D, high alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source D, and at the same time, water glass and high alkali sodium metaaluminate are used together. As an alkali source B.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this example are shown in Figure 4;

The relative crystallinity of the sample prepared in this example is 92%, and the molar ratio of silicon to aluminum (SiO ₂ /Al ₂ O ₃ ) is 5.88.

Example 5

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and its preparation method is as follows:

S1, Preparation of zeolite gel seed crystals:

S1.1 Preparation of guiding agent A

Take 20.88g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.50g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%), 5.00g NaBr and 8.56g deionized water were mixed evenly, stirred evenly at 25°C, and aged for 24h to prepare the directing agent A; among them, water glass was used as the silicon source A, and high-alkali metaaluminic acid was used Sodium is the aluminum source A, and NaBr is the sodium salt A.

Take 118.18g water glass (SiO ₂ content is 27.6wt%, Na _2O content is 8.96wt%), put it into a beaker, and place it in a 30°C water bath. Under stirring conditions, add the above-mentioned directing agent A and 5.90g high alkali. Sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 37.02g deionized water, stir for 30 minutes and then add 49.20g aluminum sulfate (Al ₂ O ₃ content is 7.6wt %) stir and mix evenly, and age for 12 hours to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 100°C for 8 hours, then filter, wash and dry to obtain NaY zeolite gel seed crystals, where , water glass is used as the silicon source B, high-alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source B, and at the same time, water glass and high-alkali sodium metaaluminate are used as the alkali source A.

Preparation of S2, high silicon to aluminum ratio NaY zeolite

S2.1 Preparation of guiding agent B

Take 16.80g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 18.65g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%) and 8.86g deionized water, stir evenly at 20°C, and age for 12 hours to prepare the guiding agent B; among them, water glass is used as the silicon source C, and high-alkali sodium metaaluminate is used as the aluminum source. C.

S2.2 obtains high silicon to aluminum ratio NaY zeolite

Take 114.32g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), put it into a beaker, and place it in a 30°C water bath. Under stirring conditions, add the above-mentioned directing agent B and 5.00g step ( The zeolite gel seed crystal prepared in 1), 13.44g overbased sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 18.51g deionized water, stir for 30 minutes Then add 29.33g aluminum sulfate (Al ₂ O ₃ content is 7.6wt%), stir and mix evenly, and age for 1 hour to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 96°C. 28h, then filter, wash and dry to obtain high silicon-to-aluminum ratio NaY zeolite, in which water glass is used as the silicon source D, high-alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source D, and water glass and high-alkali metaaluminic acid are used at the same time Sodium together acts as a base source B.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this example are shown in Figure 5;

The relative crystallinity of the sample prepared in this example is 95%, and the molar ratio of silicon to aluminum (SiO ₂ /Al ₂ O ₃ ) is 6.08.

Example 6

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and its preparation method is as follows:

S1, Preparation of zeolite gel seed crystals:

S1.1 Preparation of guiding agent A

Take 20.88g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.50g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%), 10.00g NaI and 8.56g deionized water were mixed evenly, stirred evenly at 20°C, and aged for 16h to prepare the guiding agent A; wherein, water glass was used as the silicon source A, and high-alkali partial aluminum Sodium acid is aluminum source A, and NaI is sodium salt A.

Take 108.18g of water glass (SiO ₂ content is 27.6wt%, Na _2O content is 8.96wt%), put it into a beaker, and place it in a 50°C water bath. Under stirring conditions, add the above-mentioned directing agent A and 10.90g high alkali. Sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 27.02g deionized water, stir for 30 minutes and then add 54.48g aluminum sulfate (Al ₂ O ₃ content is 7.6wt %) Stir and mix evenly, and age for 1 hour to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 96°C for 20 hours, then filter, wash and dry to obtain NaY zeolite gel seed crystals, where , water glass is used as the silicon source B, high-alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source B, and at the same time, water glass and high-alkali sodium metaaluminate are used as the alkali source A.

Preparation of S2, high silicon to aluminum ratio NaY zeolite

S2.1 Preparation of guiding agent B

Take 20.80g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), add 20.65g high-alkali sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11 wt%) and 8.36g of deionized water, stir evenly at 35°C, and age for 18 hours to prepare the guiding agent B; among them, water glass is used as the silicon source C, and high-alkali sodium metaaluminate is used as the aluminum source. C.

S2.2 obtains high silicon to aluminum ratio NaY zeolite

Take 110.32g water glass (SiO ₂ content is 27.6wt%, Na ₂ O content is 8.96wt%), put it into a beaker, and place it in a 50°C water bath. Under stirring conditions, add the above-mentioned directing agent B and 10.00g step ( The zeolite gel seed crystal prepared in 1), 10.44g high-base sodium metaaluminate (Al ₂ O ₃ content is 3.16wt%, Na ₂ O content is 21.11wt%) and 20.51g deionized water, stir for 30 minutes Then add 49.33g aluminum sulfate (Al ₂ O ₃ content is 7.6wt%), stir and mix evenly, and age for 1 hour to prepare a reaction mixture gel; put the above reaction mixture gel into a reaction kettle and crystallize it at 100°C. 26h, then filter, wash and dry to obtain high silicon to aluminum ratio NaY zeolite, in which water glass is used as the silicon source D, high-alkali sodium metaaluminate and aluminum sulfate are used as the aluminum source D, and water glass and high-alkali metaaluminic acid are used at the same time Sodium together acts as a base source B.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this example are shown in Figure 6;

The relative crystallinity of the sample prepared in this example is 90%, and the silicon-aluminum (SiO ₂ /Al ₂ O ₃ ) molar ratio is 6.25.

Example 7

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and the only difference between its preparation method and Example 1 is:

In S1.1, according to the molar ratio of 5.0×10 ^-2 sodium salt: 8Na ₂ O: Al ₂ O ₃ : 10SiO ₂ : 100H ₂ O, silicon source A, aluminum source A and sodium salt are evenly dispersed in deionized water. ; And in this embodiment, the silicon source A is alkaline silica sol; the aluminum source A is sodium metaaluminate; and the amount of sodium salt accounts for 3wt% of the directing agent A;

The temperature of the first aging treatment is 20°C, and the aging time is 12 hours;

In S1.2, according to the molar ratio of 2Na ₂ O: Al ₂ O ₃ : 6SiO ₂ : 100H ₂ O, the directing agent A, silicon source B, aluminum source B and alkali source A are evenly dispersed in deionized water; and this In the embodiment, silicon source B is alkaline silica sol; aluminum source B is sodium metaaluminate, and sodium metaaluminate and alkaline silica sol exist simultaneously as alkali source A;

The temperature of the second aging treatment is 30°C, and the aging time is 1 hour; the temperature of the first crystallization treatment is 60°C, and the crystallization time is 6 hours.

In S2.1, the silicon source C and the aluminum source C are evenly dispersed in deionized water according to the molar ratio of 10Na ₂ O: Al ₂ O ₃ : 10SiO ₂ : 100H ₂ O; and in this example, silica sol is used as Silicon source C;

The temperature of the third aging treatment is 20°C, and the aging time is 12 hours.

In S2.2, according to the molar ratio of 2Na ₂ O: Al ₂ O ₃ : 7SiO ₂ : 100H ₂ O, the directing agent B, the silicon source D, the zeolite gel seed crystal, the alkali source B and the aluminum source D are evenly dispersed in Deionized water; and in this example, silica sol is used as the silicon source D, high-alkali sodium metaaluminate and aluminum nitrate are used as the aluminum source C, and the silica sol and high-alkali sodium metaaluminate exist simultaneously as the alkali source B, And the dosage of zeolite gel seed crystal accounts for 1wt% of directing agent B;

The temperature of the fourth aging treatment is 30°C, and the aging time is 1 hour;

The time of the second crystallization treatment is 12h.

Example 8

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and the only difference between its preparation method and Example 1 is:

In S1.1, silicon source A, aluminum source A and sodium salt are evenly dispersed in deionized water according to the molar ratio of 20 sodium salt: 20Na ₂ O: Al ₂ O ₃ : 20SiO ₂ : 350H ₂ O; and this implementation In this example, silicon source A is alkaline silica sol; aluminum source A is sodium metaaluminate; and the amount of sodium salt accounts for 18wt% of directing agent A;

The temperature of the first aging treatment is 35°C, and the aging time is 24 hours.

In S1.2, according to the molar ratio of 4Na ₂ O: Al ₂ O ₃ : 15SiO ₂ : 300H ₂ O, the directing agent A, silicon source B, aluminum source B and alkali source A are evenly dispersed in deionized water; and this In the embodiment, silicon source B is alkaline silica sol; aluminum source B is sodium metaaluminate, and sodium metaaluminate and alkaline silica sol exist simultaneously as alkali source A;

The temperature of the second aging treatment is 60°C, and the aging time is 12 hours;

The temperature of the first crystallization treatment is 100°C and the time is 60h.

In S2.1, the silicon source C and aluminum source C are evenly dispersed in deionized water according to the molar ratio of 20Na ₂ O: Al ₂ O ₃ : 20SiO ₂ : 350H ₂ O; and in this example, silica sol is used as Silicon source C;

The temperature of the third aging treatment is 35°C, and the aging time is 24 hours.

In S2.2, according to the molar ratio of 4Na ₂ O: Al ₂ O ₃ : 12SiO ₂ : 300H ₂ O, the directing agent B, the silicon source D, the zeolite gel seed crystal, the alkali source B and the aluminum source D are evenly dispersed in Deionized water; and in this example, silica sol is used as the silicon source D, high-alkali sodium metaaluminate and aluminum nitrate are used as the aluminum source C, and the silica sol and high-alkali sodium metaaluminate exist simultaneously as the alkali source B, And the dosage of zeolite gel seed crystal accounts for 20wt% of directing agent B;

The temperature of the fourth aging treatment is 65°C, and the aging time is 12 hours;

The time of the second crystallization treatment is 60h.

Example 9

This embodiment provides a high silicon to aluminum ratio NaY zeolite, and the only difference between its preparation method and Example 1 is:

In this embodiment, silicon source C and silicon source D are both selected from silica gel; aluminum source C and aluminum source D are both selected from sodium metaaluminate and aluminum hydroxide.

Comparative example 1

This comparative example provides a high silicon to aluminum ratio NaY zeolite, and the only difference between its preparation method and Example 1 is:

In this comparative example, no sodium salts (NaCl, NaBr and NaI) were added, and no zeolite gel seeds were added.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this example are shown in Figure 7;

The relative crystallinity of the sample prepared in this example is 85%, and the silicon-aluminum (SiO ₂ /Al ₂ O ₃ ) molar ratio is 5.41.

Comparative example 2

This comparative example provides a high silicon to aluminum ratio NaY zeolite, and the only difference between its preparation method and Example 2 is:

In this comparative example, no sodium salts (NaCl, NaBr and NaI) were added, and no zeolite gel seeds were added.

The temperature of the second crystallization treatment is 100°C, and the crystallization time is 40 hours.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this comparative example are shown in Figure 8;

The relative crystallinity of the sample prepared in this comparative example is 70%, and it contains NaP miscellaneous crystals, and the silicon-aluminum (SiO ₂ /Al ₂ O ₃ ) molar ratio is 5.31.

Comparative example 3

This comparative example provides a high silicon to aluminum ratio NaY zeolite, and the only difference between its preparation method and Example 2 is:

In this comparative example, no sodium salt (NaCl, NaBr and NaI) is added, and no zeolite gel seed crystal is added;

The temperature of the second crystallization treatment is 100°C, and the crystallization time is 40 hours.

The XRD characterization results of the high silicon to aluminum ratio NaY zeolite prepared in this comparative example are shown in Figure 9;

The relative crystallinity of the sample prepared in this comparative example is 85%, and it contains NaP miscellaneous crystals, and the silicon-aluminum (SiO ₂ /Al ₂ O ₃ ) molar ratio is 5.30.

It should be noted that in the above-mentioned embodiments and comparative examples of the present invention, the relative crystallinity and silicon-aluminum ratio of the synthesized NaY zeolite were measured using a BRUKER D8 ADVANCE (Germany Bruker) X-ray diffractometer, and the experimental conditions were: CuKa Radiation (0.1541nm), tube voltage 30kV, tube current 20mA. The determination of relative crystallinity was carried out according to the SH/T 0340-92 standard method ("Chemical Industry Standard Compilation"), China Standards Press, published in 2000). The determination of the silicon-aluminum ratio is carried out according to the SH/T 0339-92 standard method ("Chemical Industry Standard Compilation", published by China Standard Press, 2000), and after calculating the unit cell constant of NaY zeolite according to formula (1), press Calculated by Breck-Flanigen formula: Si/Al=(25.858-α)/(α-24.191).

in,

a—Unit cell constant,

λ-CuKα1 radiation wavelength

h2+k2+l2—sum of squares of X-ray diffraction Miller indices.

The zeolite standard sample used as the crystallization standard in the Examples and Comparative Examples is from the industrial NaY reference sample, and the SiO ₂ /Al of the zeolite is measured using the X-ray diffraction method. _2O3 is _5.0 and its crystallinity is set to 100%.

Examples 1-6 of the present invention all produced NaY zeolite with high crystallinity and high silicon-aluminum ratio suitable for industrial production, and the effects were parallel. The following takes the high-silica-aluminum ratio NaY zeolite prepared in Examples 1-6 as an example. A comparative study was conducted with Comparative Examples 1-3. The specific research results are shown in Table 1:

Table 1 Examples 1-6 and Comparative Examples 1-3 relative crystallinity, silicon to aluminum ratio, unit cell constant and crystal phase analysis table

According to the XRD patterns of the samples in Figures 1 to 9, the relevant data shown in Table 1 were obtained through calculation and analysis. The results show that the NaY zeolite prepared by the present invention has the advantages of high crystallinity and high silicon-to-aluminum ratio. Zeolite is used as a post-modification raw material, and the catalyst prepared will have higher stability and more strong acid centers, and will also be more conducive to the conversion of heavy oil molecules.

Obviously, the above-mentioned embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

Claims (8)

1. The preparation method of the NaY zeolite with high silicon-aluminum ratio is characterized by comprising the following steps:

step 1, preparing zeolite gel seed crystal

According to (5.0X10) ^-2 -20) sodium salt: (8-20) Na ₂ O：Al ₂ O ₃ ：(10-20)SiO ₂ ：(100-350)H ₂ O, uniformly dispersing a silicon source A, an aluminum source A and sodium salt in an aqueous solution A, and performing first aging treatment to obtain a guiding agent A;

subsequently, according to (2-4) Na ₂ O：Al ₂ O ₃ ：(6-15)SiO ₂ ：(100-300)H ₂ Uniformly dispersing a guiding agent A, a silicon source B, an aluminum source B and an alkali source A in an aqueous solution B according to the molar ratio of O, performing a second aging treatment, and performing a first crystallization treatment at 85-100 ℃ to obtain zeolite gel seed crystals;

step 2, crystallizing to form NaY zeolite with high silicon-aluminum ratio

According to (10-20) Na ₂ O：Al ₂ O ₃ ：(10-20)SiO ₂ ：(100-350)H ₂ O mole ratio, uniformly dispersing silicon source C and aluminium source C in water solution C, and after third ageing treatment obtainingA guiding agent B;

subsequently, according to (2-4) Na ₂ O：Al ₂ O ₃ ：(7-12)SiO ₂ ：(100-300)H ₂ Uniformly dispersing a guiding agent B, a silicon source D, zeolite gel seed crystals, an alkali source B and an aluminum source D in an aqueous solution D according to the molar ratio of O, performing a second crystallization treatment at 85-100 ℃ after the fourth aging treatment, and obtaining the NaY zeolite with high silicon-aluminum ratio;

the silicon source A and the silicon source B are selected from one or two of water glass and alkaline silica sol;

the aluminum source A and the aluminum source B are selected from one or two of sodium metaaluminate and high-alkali sodium metaaluminate;

the sodium salt is one or more of NaCl, naBr and NaI;

the zeolite gel seed crystal accounts for 10-20wt% of the guiding agent B.

2. The method of claim 1, wherein the silicon source C and the silicon source D are each selected from one or more of silica sol, water glass, white carbon black, and silica gel;

the aluminum source C and the aluminum source D are selected from one or more of sodium metaaluminate, high-alkali sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide.

3. The preparation method according to claim 1, wherein the sodium salt is used in an amount of 3 to 18wt% of the guiding agent a.

4. The method according to claim 1, wherein the first aging treatment is carried out at a temperature of 20 to 35 ℃ for 12 to 24 hours;

the temperature of the second aging treatment is 30-60 ℃ and the aging time is 1-12 h;

the time of the first crystallization treatment is 6-60 h.

5. The method according to claim 1, wherein the temperature of the third aging treatment is 20 to 35 ℃ and the aging time is 12 to 24 hours;

the temperature of the fourth aging treatment is 30-65 ℃ and the aging time is 1-12 h;

the time of the second crystallization treatment is 12-60 h.

6. A high silica to alumina ratio NaY zeolite prepared by the process of any one of claims 1 to 5.

7. The NaY zeolite with high silica-alumina ratio according to claim 6, wherein the crystallinity of the NaY zeolite with high silica-alumina ratio is not less than 90% and the silica-alumina ratio is 5.5-7.0.

8. Use of a NaY zeolite of high silica alumina ratio according to claim 6 for the preparation of adsorbents and catalysts.