Method for in-situ crystallization synthesis of high crystallinity zeolite molecular sieve from aluminosilicate minerals

Abstract

The application discloses a method for synthesizing high-crystallinity zeolite molecular sieve by in-situ crystallization of aluminosilicate minerals, and belongs to the technical field of zeolite molecular sieve synthesis. The preparation steps comprise the following steps: preparing a crystal nucleus liquid containing zeolite molecular sieve microcrystals and solid-phase crystal elements; mixing the aluminosilicate minerals with the crystal nucleus liquid, and then respectively calcining at 850-1000 DEG C and 650-800 DEG C to obtain active mineral silicon sources and aluminum sources; mixing the active mineral sources with additional silicon species, NaOH, a template agent, the crystal nucleus liquid, the solid-phase crystal elements and water, and crystallizing at 90-150 DEG C, and then obtaining the high-crystallinity zeolite molecular sieve through post-processing. The crystal nucleus liquid and the solid-phase crystal elements are introduced to promote the in-situ conversion of the silicon and aluminum components in the aluminosilicate minerals into target molecular sieves, significantly improve the crystallinity of the product, reduce the synthesis cost, and are suitable for the fields of petroleum chemical industry, environmental protection and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of zeolite molecular sieve synthesis, and particularly relates to a method for synthesizing a high-crystallinity zeolite molecular sieve through in-situ crystallization of an aluminosilicate mineral. BACKGROUND

[0002] Aluminosilicate minerals are a class of layered structure minerals mainly composed of silicon oxide (SiO2) and aluminum oxide (Al2O3), and the crystal structure thereof is formed by closely connecting silicon-oxygen tetrahedral sheets and aluminum-oxygen octahedral sheets through hydrogen bonds to form a 1:1 type non-expanding layered structure. The aluminosilicate minerals mainly include mineral types such as kaolin, halloysite, dickite, perlite, and bentonite, and are widely available and low in price. The method for synthesizing a zeolite molecular sieve through in-situ crystallization of an aluminosilicate mineral is to use the aluminosilicate mineral as the main source of silicon and aluminum, and to make the silicon and aluminum species in the aluminosilicate mineral in-situ transform into a zeolite molecular sieve through in-situ crystallization under the action of a directing agent. Compared with the hydrothermal synthesis method, the method can significantly reduce the synthesis cost of the zeolite molecular sieve by using the low-cost aluminosilicate mineral as the raw material. However, the main problem of the existing method is that the crystallinity (content) of the synthesized zeolite molecular sieve is relatively low, which seriously affects the application performance of the synthesized zeolite molecular sieve. In particular, for Y-type molecular sieves and ZSM-5 zeolite molecular sieves.

[0003] Y-type molecular sieve is a kind of zeolite molecular sieve, has an eight-membered zeolite type crystal structure, an average effective pore size of about 0.74 nm, a high silicon-to-aluminum ratio, strong hydrothermal stability, excellent adsorption selectivity and catalytic activity, and is widely used in the fields of petroleum chemical industry, adsorption separation, environmental protection, and fine chemical industry. The Y-type zeolite molecular sieve is currently mainly synthesized by the hydrothermal synthesis method, which usually uses water glass as the silicon source, sodium metaaluminate or an aluminum salt as the aluminum source, and is synthesized into the Y-type zeolite molecular sieve through hydrothermal crystallization under the action of an alkali liquor and a directing agent. However, since the raw materials are all from finished chemical reagents, the synthesis cost of the Y-type zeolite molecular sieve is relatively high. The ZSM-5 zeolite molecular sieve is currently mainly synthesized by the hydrothermal synthesis method, which usually uses water glass as the silicon source, sodium metaaluminate or an aluminum salt as the aluminum source, and is synthesized through hydrothermal crystallization under the action of an alkali and a template agent. However, since the raw materials are all from finished chemical reagents, the synthesis cost of the ZSM-5 zeolite molecular sieve is increased.

[0004] Therefore, how to improve the crystallinity of the synthesized zeolite molecular sieve is a technical problem faced by the field of synthesizing a zeolite molecular sieve through in-situ crystallization of an aluminosilicate mineral. SUMMARY

[0005] In view of the above technical problems, the present application aims to provide a method for synthesizing high-crystallinity zeolite molecular sieves in situ from aluminosilicate minerals.

[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions.

[0007] The method for synthesizing high-crystallinity zeolite molecular sieves in situ from aluminosilicate minerals comprises the following steps:

[0008] (1) mixing zeolite molecular sieves, NaOH (sodium hydroxide), a silicon source, an aluminum source and water, then performing hydrothermal treatment, followed by filtration, wherein the obtained filtrate is used as a crystal nucleus liquid, and the obtained solid is dried to obtain a solid-phase crystal nucleus;

[0009] (2) mixing aluminosilicate minerals, the crystal nucleus liquid obtained in step (1) and water, drying, and then calcining at 850-1000℃ to obtain an active mineral silicon source;

[0010] (3) mixing aluminosilicate minerals, the crystal nucleus liquid obtained in step (1) and water, drying, and then calcining at 650-800℃ to obtain an active mineral aluminum source;

[0011] (4) mixing the active mineral silicon source obtained in step (2), the active mineral aluminum source obtained in step (3), an additional silicon species, NaOH, a template agent, the crystal nucleus liquid obtained in step (1), the solid-phase crystal nucleus obtained in step (1) and water, and then performing crystallization in an autoclave, followed by filtration, washing and drying to obtain the high-crystallinity zeolite molecular sieves.

[0012] In step (1), the mass ratio of the zeolite molecular sieves (dry basis), NaOH, the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3) and water is 1:(0.1-0.3):(0.05-0.5):(0-0.1):(4-8).

[0013] In step (1), the hydrothermal treatment temperature is 40-160℃, and the hydrothermal treatment time is 4-24h.

[0014] In step (1), the zeolite molecular sieves are zeolite molecular sieves with a SiO2 / Al2O3 molar ratio≥10; the silicon source is at least one of silica sol, silica gel, white carbon black and water glass, preferably water glass; and the aluminum source is at least one of aluminum sulfate, sodium aluminate, aluminum nitrate, pseudo-boehmite, boehmite and aluminum chloride, preferably sodium aluminate.

[0015] The mass ratio of the aluminosilicate mineral, the crystal nucleus liquid and water in the step (2) and step (3) is 1: (0.1-0.3): (0.5-1); the aluminosilicate mineral is at least one of kaolin, diatomite, halloysite, montmorillonite, bentonite, attapulgite, pyrophyllite and perlite.

[0016] The calcination time in the step (2) is 1-3h; the calcination time in the step (3) is 1-3h.

[0017] The dry basis mass ratio of the active mineral silicon source and the active mineral aluminum source in the step (4) is (1-10):(1-5).

[0018] The mass ratio of the active mineral silicon source and the active mineral aluminum source (dry basis), the additional silicon species (based on the mass of SiO2), NaOH, the template agent, the crystal nucleus liquid obtained in the step (1), the solid phase crystal nucleus obtained in the step (1) and water in the step (4) is 1: (0.05-0.5): (0.05-0.3): (0-0.15): (0.05-0.15): (0.01-0.10): (4-8).

[0019] The additional silicon species in the step (4) is at least one of silica sol, silica gel, white carbon black and water glass, preferably water glass; the template agent in the step (4) is at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-butylamine, triethylamine and diethylamine, preferably tetrapropylammonium hydroxide.

[0020] The crystallization temperature in the step (4) is 90-150℃, and the crystallization time is 12-48h.

[0021] In the step (1), the zeolite molecular sieve is preferably one of high-silicon USY zeolite molecular sieve or ZSM-5 zeolite molecular sieve.

[0022] In the method, the filtering, washing and drying in the step are not specially limited and can adopt the technical solutions well known by those skilled in the art.

[0023] The present application hydrothermally treats high-silica zeolite molecular sieves (such as USY, ZSM-5) with a silicon source and an aluminum source under alkaline conditions, so that part of the molecular sieve structure is dissociated, and then filtered. The filtrate is a crystal nucleus liquid containing microcrystals, and the solid is dried to form a solid-phase crystal nucleus. Both of them are used as "seeds" for subsequent crystallization. The aluminosilicate mineral is mixed with the crystal nucleus liquid and then calcined at different temperatures: 850-1000°C to produce an active mineral silicon source, and the microcrystals in the crystal nucleus liquid induce the silicon component in the mineral to transform into the target molecular sieve microstructure unit at high temperature; 650-800°C to produce an active mineral aluminum source, and the microcrystals induce the aluminum component in the mineral to transform into the target molecular sieve microstructure unit at medium temperature. The active mineral silicon source and the active mineral aluminum source are mixed with an additional silicon species, alkali, a template agent, the crystal nucleus liquid, and the solid-phase crystal nucleus in an autoclave for crystallization. The pre-set microstructure units, the crystal nucleus liquid, and the solid-phase crystal nucleus jointly act to accelerate the nucleation and growth of the target molecular sieve, and finally form a high-crystallinity product.

[0024] In the preparation of high-crystallinity Y-type zeolite molecular sieves, high-silica USY zeolite molecular sieves, a silicon source, and an aluminum source are first hydrothermally treated in an alkaline aqueous solution. During the process, on the one hand, part of the structure units of the high-silica USY zeolite molecular sieves are dissociated in the alkaline medium, and on the other hand, the silicon source and the aluminum source generate Y-type zeolite molecular sieve microstructure units (microcrystals) through a crystallization reaction under the guidance of the structure of the high-silica USY molecular sieves. Then, after filtration and separation, a crystal nucleus liquid containing high-concentration Y-type zeolite molecular sieve microcrystals and a solid-phase crystal nucleus are obtained. Then, the aluminosilicate mineral is mixed with the prepared crystal nucleus liquid and water, dried, and calcined to produce an active mineral silicon source and an active mineral aluminum source, respectively. During the above calcination process, part of the silicon and aluminum components in the aluminosilicate mineral generate Y-type molecular sieve microstructure units through a solid-phase reaction under the structure mutagenesis of the USY zeolite molecular sieve microcrystals contained in the crystal nucleus liquid, thereby pre-setting Y-type molecular sieve microstructure units in the structure of the prepared active mineral silicon source and active mineral aluminum source; finally, the above active mineral silicon source and active mineral aluminum source pre-set with Y-type molecular sieve microstructure units are used as the main silicon and aluminum sources to in-situ synthesize Y-type zeolite molecular sieves through an in-situ crystallization process under the action of an additional silicon species, NaOH, the crystal nucleus liquid, and the solid-phase crystal nucleus. In this way, as the induced crystallization active species, the pre-set Y-type molecular sieve microstructure units in the above system, as well as the USY zeolite molecular sieve microcrystals contained in the crystal nucleus liquid and the solid-phase crystal nucleus, can greatly promote the nucleation, growth, and crystallization process of Y-type zeolite molecular sieves in the in-situ crystallization process, thereby significantly improving the crystallinity of the Y-type zeolite molecular sieve product synthesized by the in-situ crystallization of aluminosilicate minerals, and imparting excellent application performance to the synthesized Y-type zeolite molecular sieves.

[0025] In the preparation of high crystallinity ZSM-5 zeolite molecular sieve, firstly, ZSM-5 zeolite molecular sieve and silicon source are subjected to hydrothermal treatment in an alkaline aqueous solution. During the hydrothermal process, on one hand, part of the structure units of the ZSM-5 zeolite molecular sieve are dissociated, and on the other hand, under the structure guiding effect of the ZSM-5 zeolite molecular sieve, SiO2 in the silicon source is transformed into ZSM-5 zeolite molecular sieve microstructure units (microcrystals). Then, after filtration and separation, a crystal nucleus liquid containing high concentration of ZSM-5 zeolite molecular sieve microcrystals and solid phase crystal units are obtained. Then, the aluminosilicate mineral is mixed with the prepared directing agent (crystal nucleus liquid) and water, dried and calcined to obtain an active mineral silicon source and an active mineral aluminum source. During the above calcination process, part of the silicon and aluminum components in the aluminosilicate mineral are transformed into ZSM-5 zeolite molecular sieve microstructure units under the structure guiding effect of the ZSM-5 zeolite molecular sieve microcrystals contained in the crystal nucleus liquid, so that the ZSM-5 zeolite molecular sieve microstructure units are prepositioned in the structure of the prepared active mineral silicon source and active mineral aluminum source. Finally, the active mineral silicon source and the active mineral aluminum source prepositioned with the ZSM-5 zeolite molecular sieve microstructure units are used as the main silicon and aluminum sources, and under the action of an additional silicon source, NaOH, a template agent and solid phase crystal units, ZSM-5 zeolite molecular sieve is synthesized through an in-situ crystallization process. In this way, as the inductive crystallization active species, the ZSM-5 zeolite molecular sieve microstructure units prepositioned in the active mineral source and the solid phase crystal units can greatly promote the nucleation, growth and crystallization process of the ZSM-5 zeolite molecular sieve in the in-situ crystallization process, thereby significantly improving the crystallinity of the aluminosilicate mineral in-situ crystallization synthesized ZSM-5 zeolite molecular sieve product, and imparting excellent application performance to the synthesized in-situ crystallization ZSM-5 zeolite molecular sieve.

[0026] Compared with the prior art, the present application has the following beneficial effects:

[0027] (1) By introducing the crystal nucleus liquid and the solid phase crystal units, the nucleation, growth and crystallization process of the zeolite molecular sieve are promoted, and the crystallinity of the synthesized Y-type and ZSM-5 zeolite molecular sieve is significantly higher than that of the prior art. The crystallinity of the Y-type zeolite molecular sieve synthesized by the present application is as high as 66%, while the highest crystallinity of the prior art is 46%; the crystallinity of the ZSM-5 zeolite molecular sieve is as high as 62%. The high crystallinity imparts the zeolite molecular sieve with more excellent adsorption selectivity, catalytic activity and hydrothermal stability, and widens the application range of the zeolite molecular sieve in the fields of petroleum chemical industry, adsorption separation, environmental protection and the like.

[0028] (2) The present application uses widely available and low-cost aluminosilicate minerals (such as kaolin, halloysite, etc.) as the main silicon and aluminum sources, instead of the finished chemical reagents used in the traditional hydrothermal synthesis, thereby greatly reducing the raw material cost; the present application can be adapted to different types of aluminosilicate minerals and target zeolite molecular sieves by adjusting the raw material ratio, calcination temperature, crystallization conditions and the like parameters. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 XRD pattern of Y-type zeolite molecular sieve (C1) synthesized in Example 1 of the present application.

[0030] Figure 2 XRD pattern of Y-type zeolite molecular sieve (D1) synthesized in Comparative Example 1 of the present application.

[0031] Figure 3 XRD pattern of ZSM-5-type zeolite molecular sieve (C10) synthesized in Example 10 of the present application.

[0032] Figure 4 XRD pattern of ZSM-5-type zeolite molecular sieve (D4) synthesized in Comparative Example 4 of the present application. DETAILED DESCRIPTION

[0033] The technical solutions in the present application will be described clearly and completely below in combination with the examples in the present application.

[0034] USY zeolite molecular sieve: Catalyst Factory of Nankai University;

[0035] ZSM-5 zeolite molecular sieve: Catalyst Factory of Nankai University.

[0036] (1) Specifications of raw materials

[0037] Kaolin (solid content 85.6%), halloysite (solid content 86.7%), bentonite (solid content 76.8%), USY zeolite molecular sieve (solid content 89.7%, SiO2 / Al2O3=11), ZSM-5 zeolite molecular sieve (solid content 89.7%, SiO2 / Al2O3=40), water glass (modulus 3.3, SiO2 content 20%) and directing agent (15SiO2:Al2O3:15Na2O:320H2O), qualified industrial products.

[0038] Sodium hydroxide (NaOH), sodium aluminate (NaAlO2, Al2O3 content 62%) analytical reagent, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.; tetrapropylammonium hydroxide (TPAOH), analytical reagent, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0039] (2) Analysis and testing

[0040] The phase and crystallinity of the product were analyzed and tested on a D / max-2200PC X-ray diffractometer produced by Rigaku Company, Japan.

[0041] Example 1

[0042] The method for synthesizing a high-crystallinity zeolite molecular sieve in situ crystallization of aluminosilicate minerals comprises the following steps:

[0043] (1) 50 g of USY zeolite molecular sieve (dry basis), 5 g of NaOH, 25 g of water glass, 0.81 g of sodium metaaluminate and 200 g of water were mixed and hydrothermally treated (40°C, 24 h), and then filtered, the obtained filtrate was used as the crystal nucleus liquid, and the obtained solid was dried and used as the solid phase crystal nucleus;

[0044] (2) 1000 g of kaolin (dry basis), 100 g of the crystal nucleus liquid obtained in step (1) and 500 g of water were mixed, dried, and then calcined at 850°C for 3 h to obtain an active mineral silicon source;

[0045] (3) 1000 g of kaolin (dry basis), 200 g of the crystal nucleus liquid obtained in step (1) and 700 g of water were mixed, dried, and then calcined at 800°C for 1 h to obtain an active mineral aluminum source;

[0046] (4) 250 g of the active mineral silicon source (dry basis) obtained in step (2), 250 g of the active mineral aluminum source (dry basis) obtained in step (3), 250 g of water glass, 25 g of NaOH, 25 g of the crystal nucleus liquid obtained in step (1), 12.5 g of the solid phase crystal nucleus obtained in step (1) and 2000 g of water were mixed and placed in an autoclave for crystallization (90°C, 48 h), and then filtered, washed and dried to obtain the Y-type zeolite molecular sieve C1.

[0047] Example 2

[0048] A method for in-situ crystallization synthesis of a high-crystallinity zeolite molecular sieve from an aluminosilicate mineral, comprising the following steps:

[0049] (1) 70 g of USY zeolite molecular sieve (dry basis), 14 g of NaOH, 105 g of water glass, 5.65 g of sodium metaaluminate and 420 g of water were mixed and hydrothermally treated (70°C, 12 h), and then filtered, the obtained filtrate was used as the crystal nucleus liquid, and the obtained solid was dried and used as the solid phase crystal nucleus;

[0050] (2) 1000 g of kaolin (dry basis), 200 g of the crystal nucleus liquid obtained in step (1) and 700 g of water were mixed, dried, and then calcined at 900°C for 2 h to obtain an active mineral silicon source;

[0051] (3) 1000 g of kaolin (dry basis), 300 g of the crystal nucleus liquid obtained in step (1) and 1000 g of water were mixed, dried, and then calcined at 700°C for 2 h to obtain an active mineral aluminum source;

[0052] (4) 350 g of the active mineral silicon source (dry basis) obtained in step (2), 150 g of the active mineral aluminum source (dry basis) obtained in step (3), 750 g of water glass, 100 g of NaOH, 75 g of the crystal nucleus liquid obtained in step (1), 50 g of the solid-phase crystal nucleus obtained in step (1), and 4000 g of water were mixed and placed in an autoclave for crystallization (130°C, 16 h), and then after filtration, washing, and drying, the Y-type zeolite molecular sieve C3 was obtained.

[0053] Example 3

[0054] A method for synthesizing a high-crystallinity zeolite molecular sieve by in-situ crystallization of aluminosilicate minerals, comprising the following steps:

[0055] (1) 90 g of USY zeolite molecular sieve (dry basis), 27 g of NaOH, 225 g of water glass, 14.52 g of sodium metaaluminate, and 720 g of water were mixed and hydrothermally treated (95°C, 4 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried and used as a solid-phase crystal nucleus;

[0056] (2) 1000 g of kaolin (dry basis), 300 g of the crystal nucleus liquid obtained in step (1), and 1000 g of water were mixed, dried, and then calcined at 1000°C for 1 h to obtain an active mineral silicon source;

[0057] (3) 1000 g of kaolin (dry basis), 100 g of the crystal nucleus liquid obtained in step (1), and 500 g of water were mixed, dried, and then calcined at 650°C for 3 h to obtain an active mineral aluminum source;

[0058] (4) 350 g of the active mineral silicon source (dry basis) obtained in step (2), 150 g of the active mineral aluminum source (dry basis) obtained in step (3), 750 g of water glass, 100 g of NaOH, 75 g of the crystal nucleus liquid obtained in step (1), 50 g of the solid-phase crystal nucleus obtained in step (1), and 4000 g of water were mixed and placed in an autoclave for crystallization (130°C, 16 h), and then after filtration, washing, and drying, the Y-type zeolite molecular sieve C3 was obtained.

[0059] Example 4

[0060] A method for synthesizing a high-crystallinity zeolite molecular sieve by in-situ crystallization of aluminosilicate minerals, comprising the following steps:

[0061] (1) 50 g of USY zeolite molecular sieve (dry basis), 7 g of NaOH, 75 g of water glass, 4.03 g of sodium metaaluminate, and 300 g of water were mixed and hydrothermally treated (70°C, 12 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried and used as a solid-phase crystal nucleus;

[0062] (2) 1000 g of halloysite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 900 °C for 2 h to obtain an active mineral silicon source;

[0063] (3) 1000 g of halloysite (dry basis), 100 g of the crystal nucleus liquid obtained in step (1), and 500 g of water were mixed, dried, and then calcined at 700 °C for 2 h to obtain an active mineral aluminum source;

[0064] (4) 300 g of the active mineral silicon source (dry basis) obtained in step (2), 200 g of the active mineral aluminum source (dry basis) obtained in step (3), 500 g of water glass, 50 g of NaOH, 50 g of the crystal nucleus liquid obtained in step (1), 25 g of the solid-phase crystal nucleus obtained in step (1), and 3000 g of water were mixed and then placed in an autoclave for crystallization (at 110 °C for 24 h), and then filtered, washed, and dried to obtain the Y-type zeolite molecular sieve C4.

[0065] Example 5

[0066] The method for in-situ crystallization of aluminosilicate minerals to synthesize high-crystallinity zeolite molecular sieves comprises the following steps:

[0067] (1) 70 g of USY zeolite molecular sieve (dry basis), 18 g of NaOH, 175 g of water glass, 11.29 g of sodium metaaluminate, and 560 g of water were mixed and then hydrothermally treated (at 95 °C for 4 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid-phase crystal nucleus;

[0068] (2) 1000 g of halloysite (dry basis), 300 g of the crystal nucleus liquid obtained in step (1), and 1000 g of water were mixed, dried, and then calcined at 1000 °C for 1 h to obtain an active mineral silicon source;

[0069] (3) 1000 g of halloysite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 650 °C for 3 h to obtain an active mineral aluminum source;

[0070] (4) 350 g of the active mineral silicon source (dry basis) obtained in step (2), 150 g of the active mineral aluminum source (dry basis) obtained in step (3), 750 g of water glass, 100 g of NaOH, 75 g of the crystal nucleus liquid obtained in step (1), 50 g of the solid-phase crystal nucleus obtained in step (1), and 4000 g of water were mixed and then placed in an autoclave for crystallization (at 130 °C for 16 h), and then filtered, washed, and dried to obtain the Y-type zeolite molecular sieve C5.

[0071] Example 6

[0072] The method for in-situ crystallization of aluminosilicate minerals to synthesize high-crystallinity zeolite molecular sieves comprises the following steps:

[0073] (1) 90 g of USY zeolite molecular sieve (dry basis), 15 g of NaOH, 45 g of water glass, 1.45 g of sodium metaaluminate and 360 g of water were mixed and hydrothermally treated (40°C, 24 h), and then filtered, the obtained filtrate was used as the crystal nucleus liquid, and the obtained solid was dried and used as the solid phase crystal nucleus;

[0074] (2) 1000 g of halloysite (dry basis), 100 g of the crystal nucleus liquid obtained in step (1) and 500 g of water were mixed, dried, and then calcined at 850°C for 3 h to obtain an active mineral silicon source;

[0075] (3) 1000 g of halloysite (dry basis), 300 g of the crystal nucleus liquid obtained in step (1) and 1000 g of water were mixed, dried, and then calcined at 800°C for 1 h to obtain an active mineral aluminum source;

[0076] (4) 250 g of the active mineral silicon source (dry basis) obtained in step (2), 250 g of the active mineral aluminum source (dry basis) obtained in step (3), 250 g of water glass, 25 g of NaOH, 25 g of the crystal nucleus liquid obtained in step (1), 12.5 g of the solid phase crystal nucleus obtained in step (1) and 2000 g of water were mixed and placed in an autoclave for crystallization (90°C, 48 h), and then filtered, washed and dried to obtain the Y-type zeolite molecular sieve C6.

[0077] Example 7

[0078] The method for in-situ crystallization synthesis of high-crystallinity zeolite molecular sieve from aluminosilicate minerals comprises the following steps:

[0079] (1) 50 g of USY zeolite molecular sieve (dry basis), 9 g of NaOH, 125 g of water glass, 8.06 g of sodium metaaluminate and 400 g of water were mixed and hydrothermally treated (95°C, 4 h), and then filtered, the obtained filtrate was used as the crystal nucleus liquid, and the obtained solid was dried and used as the solid phase crystal nucleus;

[0080] (2) 1000 g of bentonite (dry basis), 300 g of the crystal nucleus liquid obtained in step (1) and 1000 g of water were mixed, dried, and then calcined at 1000°C for 1 h to obtain an active mineral silicon source;

[0081] (3) 1000 g of bentonite (dry basis), 300 g of the crystal nucleus liquid obtained in step (1) and 1000 g of water were mixed, dried, and then calcined at 650°C for 3 h to obtain an active mineral aluminum source;

[0082] (4) 350 g of the active mineral silicon source (dry basis) obtained in step (2), 150 g of the active mineral aluminum source (dry basis) obtained in step (3), 750 g of water glass, 100 g of NaOH, 75 g of the crystal nucleus liquid obtained in step (1), 50 g of the solid-phase crystal nucleus obtained in step (1), and 4000 g of water were mixed and placed in an autoclave for crystallization (130°C, 16 h), and then after filtration, washing, and drying, the Y-type zeolite molecular sieve C7 was obtained.

[0083] Example 8

[0084] A method for synthesizing a high-crystallinity zeolite molecular sieve by in-situ crystallization of aluminosilicate minerals, comprising the following steps:

[0085] (1) 70 g of USY zeolite molecular sieve (dry basis), 10 g of NaOH, 35 g of water glass, 1.13 g of sodium metaaluminate, and 280 g of water were mixed and hydrothermally treated (40°C, 24 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried and used as a solid-phase crystal nucleus;

[0086] (2) 1000 g of bentonite (dry basis), 100 g of the crystal nucleus liquid obtained in step (1), and 500 g of water were mixed, dried, and then calcined at 850°C for 3 h to obtain an active mineral silicon source;

[0087] (3) 1000 g of bentonite (dry basis), 100 g of the crystal nucleus liquid obtained in step (1), and 500 g of water were mixed, dried, and then calcined at 800°C for 1 h to obtain an active mineral aluminum source;

[0088] (4) 250 g of the active mineral silicon source (dry basis) obtained in step (2), 250 g of the active mineral aluminum source (dry basis) obtained in step (3), 250 g of water glass, 25 g of NaOH, 25 g of the crystal nucleus liquid obtained in step (1), 12.5 g of the solid-phase crystal nucleus obtained in step (1), and 2000 g of water were mixed and placed in an autoclave for crystallization (90°C, 48 h), and then after filtration, washing, and drying, the Y-type zeolite molecular sieve C8 was obtained.

[0089] Example 9

[0090] A method for synthesizing a high-crystallinity zeolite molecular sieve by in-situ crystallization of aluminosilicate minerals, comprising the following steps:

[0091] (1) 90 g of USY zeolite molecular sieve (dry basis), 21 g of NaOH, 135 g of water glass, 7.26 g of sodium metaaluminate, and 540 g of water were mixed and hydrothermally treated (70°C, 12 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried and used as a solid-phase crystal nucleus;

[0092] (2) 1000 g of bentonite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 900 °C for 2 h to obtain an active mineral silicon source;

[0093] (3) 1000 g of bentonite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 700 °C for 2 h to obtain an active mineral aluminum source;

[0094] (4) 300 g of the active mineral silicon source (dry basis) obtained in step (2), 200 g of the active mineral aluminum source (dry basis) obtained in step (3), 500 g of water glass, 50 g of NaOH, 50 g of the crystal nucleus liquid obtained in step (1), 25 g of the solid-phase crystal nucleus obtained in step (1), and 3000 g of water were mixed and then placed in an autoclave for crystallization (110 °C, 24 h), and then filtered, washed, and dried to obtain the Y-type zeolite molecular sieve C9.

[0095] Example 10

[0096] The method for in-situ crystallization of aluminosilicate minerals to synthesize high-crystallinity zeolite molecular sieves comprises the following steps:

[0097] (1) 50 g of ZSM-5 zeolite molecular sieve (dry basis), 5 g of NaOH, 25 g of water glass, and 200 g of water were mixed and then placed in an autoclave for hydrothermal treatment (80 °C, 24 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid-phase crystal nucleus;

[0098] (2) 1000 g of kaolin (dry basis), 100 g of the crystal nucleus liquid obtained in step (1), and 500 g of water were mixed, dried, and then calcined at 850 °C for 3 h to obtain an active mineral silicon source;

[0099] (3) 1000 g of kaolin (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 800 °C for 1 h to obtain an active mineral aluminum source;

[0100] (4) 900 g of the active mineral silicon source (dry basis) obtained in step (2), 100 g of the active mineral aluminum source (dry basis) obtained in step (3), 500 g of water glass, 100 g of NaOH, 50 g of TPAOH, 10 g of the solid-phase crystal nucleus obtained in step (1), and 4000 g of water were mixed and then placed in an autoclave for crystallization (100 °C, 48 h), and then filtered, washed, and dried to obtain the ZSM-5 zeolite molecular sieve C10.

[0101] Example 11

[0102] The method for in-situ crystallization of aluminosilicate minerals to synthesize high-crystallinity zeolite molecular sieves comprises the following steps:

[0103] (1) 75 g of ZSM-5 zeolite molecular sieve (dry basis), 15 g of NaOH, 112.5 g of water glass and 450 g of water were mixed and placed in an autoclave for hydrothermal treatment (130°C, 12 h), and then filtered, the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid-phase crystal nucleus;

[0104] (2) 1000 g of kaolin (dry basis), 200 g of the crystal nucleus liquid obtained in step (1) and 700 g of water were mixed, dried, and then calcined at 900°C for 2 h to obtain an active mineral silicon source;

[0105] (3) 1000 g of kaolin (dry basis), 300 g of the crystal nucleus liquid obtained in step (1) and 1000 g of water were mixed, dried, and then calcined at 700°C for 2 h to obtain an active mineral aluminum source;

[0106] (4) 750 g of the active mineral silicon source obtained in step (2) (dry basis), 250 g of the active mineral aluminum source obtained in step (3) (dry basis), 1500 g of water glass, 200 g of NaOH, 100 g of TPAOH, 50 g of the solid-phase crystal nucleus obtained in step (1) and 6000 g of water were mixed and placed in an autoclave for crystallization (120°C, 24 h), and then filtered, washed and dried to obtain the ZSM-5 zeolite molecular sieve C11.

[0107] Example 12

[0108] A method for in-situ crystallization synthesis of a high-crystallinity zeolite molecular sieve from an aluminosilicate mineral, comprising the following steps:

[0109] (1) 100 g of ZSM-5 zeolite molecular sieve, 30 g of NaOH, 250 g of water glass and 800 g of water were mixed and placed in an autoclave for hydrothermal treatment (160°C, 6 h), and then filtered, the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid-phase crystal nucleus;

[0110] (2) 1000 g of kaolin (dry basis), 300 g of the crystal nucleus liquid obtained in step (1) and 1000 g of water were mixed, dried, and then calcined at 1000°C for 1 h to obtain an active mineral silicon source;

[0111] (3) 1000 g of kaolin (dry basis), 100 g of the crystal nucleus liquid obtained in step (1) and 500 g of water were mixed, dried, and then calcined at 650°C for 3 h to obtain an active mineral aluminum source;

[0112] (4) 750 g of the active mineral silicon source (dry basis) obtained in step (2), 250 g of the active mineral aluminum source (dry basis) obtained in step (3), 1500 g of water glass, 200 g of NaOH, 100 g of TPAOH, 50 g of the solid phase crystal nucleus obtained in step (1), and 6000 g of water were mixed and placed in an autoclave for crystallization (130°C, 24 h), and then after filtration, washing, and drying, the ZSM-5 zeolite molecular sieve C13 was obtained.

[0113] Example 13

[0114] A method for synthesizing a high-crystallinity zeolite molecular sieve by in-situ crystallization of aluminosilicate minerals, comprising the following steps:

[0115] (1) 75 g of ZSM-5 zeolite molecular sieve (dry basis), 22.5 g of NaOH, 187.5 g of water glass, and 600 g of water were mixed and placed in an autoclave for hydrothermal treatment (160°C, 6 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to be used as a solid phase crystal nucleus;

[0116] (2) 1000 g of halloysite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 900°C for 2 h to obtain an active mineral silicon source;

[0117] (3) 1000 g of halloysite (dry basis), 100 g of the crystal nucleus liquid obtained in step (1), and 500 g of water were mixed, dried, and then calcined at 700°C for 2 h to obtain an active mineral aluminum source;

[0118] (4) 750 g of the active mineral silicon source (dry basis) obtained in step (2), 250 g of the active mineral aluminum source (dry basis) obtained in step (3), 1500 g of water glass, 200 g of NaOH, 100 g of TPAOH, 50 g of the solid phase crystal nucleus obtained in step (1), and 6000 g of water were mixed and placed in an autoclave for crystallization (130°C, 24 h), and then after filtration, washing, and drying, the ZSM-5 zeolite molecular sieve C13 was obtained.

[0119] Example 14

[0120] A method for synthesizing a high-crystallinity zeolite molecular sieve by in-situ crystallization of aluminosilicate minerals, comprising the following steps:

[0121] (1) 75 g of ZSM-5 zeolite molecular sieve (dry basis), 22.5 g of NaOH, 187.5 g of water glass, and 600 g of water were mixed and placed in an autoclave for hydrothermal treatment (160°C, 6 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to be used as a solid phase crystal nucleus;

[0122] (2) 1000 g of halloysite (dry basis), 300 g of the crystal nucleus liquid obtained in step (1), and 1000 g of water were mixed, dried, and then calcined at 1000 °C for 1 h to obtain an active mineral silicon source;

[0123] (3) 1000 g of halloysite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 650 °C for 3 h to obtain an active mineral aluminum source;

[0124] (4) 600 g of the active mineral silicon source (dry basis) obtained in step (2), 400 g of the active mineral aluminum source (dry basis) obtained in step (3), 2500 g of water glass, 300 g of NaOH, 150 g of TPAOH, 100 g of the solid-phase crystal nucleus obtained in step (1), and 8000 g of water were mixed and then placed in an autoclave for crystallization (150 °C for 12 h), and then filtered, washed, and dried to obtain the ZSM-5 zeolite molecular sieve C14.

[0125] Example 15

[0126] A method for in-situ crystallization synthesis of a high-crystallinity zeolite molecular sieve from an aluminosilicate mineral includes the following steps:

[0127] (1) 100 g of ZSM-5 zeolite molecular sieve (dry basis), 10 g of NaOH, 50 g of water glass, and 400 g of water were mixed and then placed in an autoclave for hydrothermal treatment (80 °C for 24 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid-phase crystal nucleus;

[0128] (2) 1000 g of halloysite (dry basis), 100 g of the crystal nucleus liquid obtained in step (1), and 500 g of water were mixed, dried, and then calcined at 850 °C for 3 h to obtain an active mineral silicon source;

[0129] (3) 1000 g of halloysite (dry basis), 300 g of the crystal nucleus liquid obtained in step (1), and 1000 g of water were mixed, dried, and then calcined at 800 °C for 1 h to obtain an active mineral aluminum source;

[0130] (4) 900 g of the active mineral silicon source (dry basis) obtained in step (2), 100 g of the active mineral aluminum source (dry basis) obtained in step (3), 500 g of water glass, 100 g of NaOH, 50 g of TPAOH, 10 g of the solid-phase crystal nucleus obtained in step (1), and 4000 g of water were mixed and then placed in an autoclave for crystallization (100 °C for 48 h), and then filtered, washed, and dried to obtain the ZSM-5 zeolite molecular sieve C15.

[0131] Example 16

[0132] A method for in-situ crystallization synthesis of a high-crystallinity zeolite molecular sieve from an aluminosilicate mineral includes the following steps:

[0133] (1) 50 g ZSM-5 zeolite molecular sieve (dry basis), 15 g NaOH, 125 g water glass and 400 g water were mixed and placed in an autoclave for hydrothermal treatment (160°C, 6 h), and then filtered, the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid-phase crystal nucleus;

[0134] (2) 1000 g bentonite (dry basis), 300 g crystal nucleus liquid obtained in step (1) and 1000 g water were mixed, dried, and then calcined at 1000°C for 1 h to obtain an active mineral silicon source;

[0135] (3) 1000 g bentonite (dry basis), 300 g crystal nucleus liquid obtained in step (1) and 1000 g water were mixed, dried, and then calcined at 650°C for 3 h to obtain an active mineral aluminum source;

[0136] (4) 600 g active mineral silicon source (dry basis) obtained in step (2), 400 g active mineral aluminum source (dry basis) obtained in step (3), 2500 g water glass, 300 g NaOH, 150 g TPAOH, 100 g solid-phase crystal nucleus obtained in step (1) and 8000 g water were mixed and placed in an autoclave for crystallization (150°C, 12 h), and then filtered, washed and dried to obtain the ZSM-5 zeolite molecular sieve C16.

[0137] Example 17

[0138] A method for in-situ crystallization synthesis of a high-crystallinity zeolite molecular sieve from an aluminosilicate mineral, comprising the following steps:

[0139] (1) 75 g ZSM-5 zeolite molecular sieve (dry basis), 7.5 g NaOH, 37.5 g water glass and 300 g water were mixed and placed in an autoclave for hydrothermal treatment (80°C, 24 h), and then filtered, the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid-phase crystal nucleus;

[0140] (2) 1000 g bentonite (dry basis), 100 g crystal nucleus liquid obtained in step (1) and 500 g water were mixed, dried, and then calcined at 850°C for 3 h to obtain an active mineral silicon source;

[0141] (3) 1000 g bentonite (dry basis), 100 g crystal nucleus liquid obtained in step (1) and 500 g water were mixed, dried, and then calcined at 800°C for 1 h to obtain an active mineral aluminum source;

[0142] (4) 900 g of the active mineral silicon source (dry basis) obtained in step (2), 100 g of the active mineral aluminum source (dry basis) obtained in step (3), 500 g of water glass, 100 g of NaOH, 50 g of TPAOH, 10 g of the solid phase crystal nucleus obtained in step (1), and 4000 g of water were mixed and placed in an autoclave for crystallization (100°C, 48 h), and then after filtration, washing, and drying, the ZSM-5 zeolite molecular sieve C17 was obtained.

[0143] Example 18

[0144] A method for in-situ crystallization synthesis of a high-crystallinity zeolite molecular sieve from an aluminosilicate mineral, comprising the following steps:

[0145] (1) 100 g of ZSM-5 zeolite molecular sieve (dry basis), 20 g of NaOH, 150 g of water glass, and 600 g of water were mixed and hydrothermally treated in an autoclave (130°C, 12 h), and then filtered, and the obtained filtrate was used as a crystal nucleus liquid, and the obtained solid was dried to obtain a solid phase crystal nucleus;

[0146] (2) 1000 g of bentonite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 900°C for 2 h to obtain an active mineral silicon source;

[0147] (3) 1000 g of bentonite (dry basis), 200 g of the crystal nucleus liquid obtained in step (1), and 700 g of water were mixed, dried, and then calcined at 700°C for 2 h to obtain an active mineral aluminum source;

[0148] (4) 750 g of the active mineral silicon source (dry basis) obtained in step (2), 250 g of the active mineral aluminum source (dry basis) obtained in step (3), 1500 g of water glass, 200 g of NaOH, 100 g of TPAOH, 50 g of the solid phase crystal nucleus obtained in step (1), and 6000 g of water were mixed and placed in an autoclave for crystallization (130°C, 24 h), and then after filtration, washing, and drying, the ZSM-5 zeolite molecular sieve C18 was obtained.

[0149] Comparative Example 1

[0150] A method for synthesizing a zeolite molecular sieve, comprising the following steps:

[0151] (1) 1000 g of kaolin (dry basis) was calcined at 850°C for 3 h to obtain an active mineral silicon source;

[0152] (2) 1000 g of kaolin (dry basis) was calcined at 800°C for 1 h to obtain an active mineral aluminum source;

[0153] (3) 300 g of the active mineral silicon source (dry basis) obtained in step (1), 200 g of the active mineral aluminum source (dry basis) obtained in step (2), 500 g of water glass, 50 g of NaOH, 50 g of the directing agent, and 3000 g of water were mixed and placed in an autoclave for crystallization (110°C, 24 h), and then after filtration, washing, and drying, Comparative Y-type zeolite molecular sieve D2 was obtained.

[0154] Comparative Example 2

[0155] A method for preparing a zeolite molecular sieve, comprising the following steps:

[0156] (1) 1000 g of halloysite (dry basis) was calcined at 900°C for 2 h to obtain an active mineral silicon source;

[0157] (2) 1000 g of halloysite (dry basis) was calcined at 700°C for 2 h to obtain an active mineral aluminum source;

[0158] (3) 300 g of the active mineral silicon source (dry basis) obtained in step (1), 200 g of the active mineral aluminum source (dry basis) obtained in step (2), 500 g of water glass, 50 g of NaOH, 50 g of the directing agent, and 3000 g of water were mixed and placed in an autoclave for crystallization (110°C, 24 h), and then after filtration, washing, and drying, Comparative Y-type zeolite molecular sieve D2 was obtained.

[0159] Comparative Example 3

[0160] A method for preparing a zeolite molecular sieve, comprising the following steps:

[0161] (1) 1000 g of bentonite (dry basis) was calcined at 1000°C for 1 h to obtain an active mineral silicon source;

[0162] (2) 1000 g of bentonite (dry basis) was calcined at 650°C for 3 h to obtain an active mineral aluminum source;

[0163] (3) 350 g of the active mineral silicon source (dry basis) obtained in step (1), 150 g of the active mineral aluminum source (dry basis) obtained in step (2), 750 g of water glass, 100 g of NaOH, 75 g of the directing agent, and 4000 g of water were mixed and placed in an autoclave for crystallization (130°C, 16 h), and then after filtration, washing, and drying, Comparative Y-type zeolite molecular sieve D3 was obtained.

[0164] Comparative Example 4

[0165] A method for preparing a zeolite molecular sieve, comprising the following steps:

[0166] (1) 1000 g of kaolin (dry basis) was calcined at 850°C for 3 h to obtain an active mineral silicon source;

[0167] (2) 1000 g kaolin (dry basis) was calcined at 800 °C for 1 h to obtain an active mineral aluminum source;

[0168] (3) 900 g of the active mineral silicon source (dry basis) obtained in step (1), 100 g of the active mineral aluminum source (dry basis) obtained in step (2), 500 g of water glass, 100 g of NaOH, 50 g of TPAOH and 4000 g of water were mixed and then placed in an autoclave for crystallization (100 °C for 48 h). After filtration, washing and drying, comparative ZSM-5 zeolite molecular sieve D4 was obtained.

[0169] Comparative Example 5

[0170] A method for preparing a zeolite molecular sieve, comprising the following steps:

[0171] (1) 1000 g of halloysite (dry basis) was calcined at 900 °C for 2 h to obtain an active mineral silicon source;

[0172] (2) 1000 g of halloysite (dry basis) was calcined at 700 °C for 2 h to obtain an active mineral aluminum source;

[0173] (3) 750 g of the active mineral silicon source (dry basis) obtained in step (1), 250 g of the active mineral aluminum source (dry basis) obtained in step (2), 1500 g of water glass, 200 g of NaOH, 100 g of TPAOH and 6000 g of water were mixed and then placed in an autoclave for crystallization (130 °C for 24 h). After filtration, washing and drying, comparative ZSM-5 zeolite molecular sieve D5 was obtained.

[0174] Comparative Example 6

[0175] A method for preparing a zeolite molecular sieve, comprising the following steps:

[0176] (1) 1000 g of bentonite (dry basis) was calcined at 1000 °C for 1 h to obtain an active mineral silicon source;

[0177] (2) 1000 g of bentonite (dry basis) was calcined at 650 °C for 3 h to obtain an active mineral aluminum source;

[0178] (3) 600 g of the active mineral silicon source (dry basis) obtained in step (1), 400 g of the active mineral aluminum source (dry basis) obtained in step (2), 2500 g of water glass, 300 g of NaOH, 150 g of TPAOH and 8000 g of water were mixed and then placed in an autoclave for crystallization (150 °C for 12 h). After filtration, washing and drying, comparative ZSM-5 zeolite molecular sieve D6 was obtained.

[0179] The XRD pattern of the Y-type zeolite molecular sieve (C1) synthesized in Example 1 is shown in Figure 1 .

[0180] The XRD pattern of the Y-type zeolite molecular sieve (D1) synthesized in Comparative Example 1 is shown in Figure 2

[0181] The XRD pattern of the ZSM-5 zeolite molecular sieve (C10) synthesized in Example 10 is shown in Figure 3

[0182] The XRD pattern of the ZSM-5 zeolite molecular sieve (D4) synthesized in Comparative Example 4 is shown in Figure 4

[0183] The crystallinity of the Y-type zeolite molecular sieves synthesized in Examples 1-9 and Comparative Examples 1-3 is shown in Table 1.

[0184] The crystallinity of the ZSM-5 zeolite molecular sieves synthesized in Examples 10-18 and Comparative Examples 4-6 is shown in Table 2.

[0185] Table 1: Crystallinity of Y-type zeolite molecular sieves synthesized in Examples 1-9 and Comparative Examples 1-3

[0186]

[0187] As shown in Table 1, the Y-type zeolite molecular sieves synthesized by the method of the present application have significantly higher crystallinity than the Y-type zeolite molecular sieves synthesized by the prior art method, indicating that the method of the present application can significantly increase the crystallinity of the Y-type zeolite molecular sieves synthesized in situ from aluminosilicate minerals, thereby being able to endow the synthesized Y-type zeolite molecular sieves with excellent application performance.

[0188] Table 2: Crystallinity of ZSM-5 zeolite molecular sieves synthesized in Examples 10-18 and Comparative Examples 4-6

[0189]

[0190] As shown in Table 2, the ZSM-5 zeolite molecular sieves synthesized by the method of the present application have significantly higher crystallinity than the ZSM-5 zeolite molecular sieves synthesized by the prior art method, indicating that the method of the present application can significantly increase the crystallinity of the ZSM-5 zeolite molecular sieves synthesized in situ from aluminosilicate minerals, thereby being able to endow the synthesized ZSM-5 zeolite molecular sieves with excellent application performance.​​​

Claims

1. A method for in-situ crystallization of aluminosilicate minerals to synthesize highly crystalline zeolite molecular sieves, characterized in that, Includes the following steps: (1) After mixing zeolite molecular sieve, NaOH, silicon source, aluminum source and water, the mixture is hydrothermally treated and then filtered. The resulting filtrate is used as the nucleation liquid, and the resulting solid is dried to serve as the solid phase crystal. (2) Mix the aluminosilicate mineral, the nucleation solution obtained in step (1) and water, dry them, and then calcine them at 850~1000℃ to obtain the active mineral silicon source; (3) Mix the aluminosilicate mineral, the nucleation solution obtained in step (1) and water, dry them, and then calcine them at 650~800℃ to obtain an active mineral aluminum source; (4) The active mineral silicon source obtained in step (2), the active mineral aluminum source obtained in step (3), the added silicon species, NaOH, template agent, the crystal nucleus liquid obtained in step (1), the solid phase crystal obtained in step (1) and water are mixed and placed in a high pressure vessel for crystallization. After filtration, washing and drying, a high crystallinity zeolite molecular sieve is obtained. In step (1), the mass ratio of zeolite molecular sieve, NaOH, silicon source, aluminum source and water is 1:(0.1~0.3):(0.05~0.5):(0~0.1):(4~8); In step (1), the zeolite molecular sieve is a zeolite molecular sieve with a SiO2 / Al2O3 molar ratio ≥10; the zeolite molecular sieve is ZSM-5 zeolite molecular sieve or USY zeolite molecular sieve; the silicon source is at least one of silica sol, silica gel, silica fume and water glass; the aluminum source is at least one of aluminum sulfate, sodium aluminate, aluminum nitrate, boehmite, boehmite and aluminum chloride. In steps (2) and (3), the mass ratio of aluminosilicate minerals, nucleation solution and water is 1:(0.1~0.3):(0.5~1); the aluminosilicate minerals are at least one of kaolin, diatomite, halloysite, montmorillonite, bentonite, attapulgite, pyrophyllite and perlite. In step (4), the dry basis mass ratio of the active mineral silicon source and the active mineral aluminum source is (1~10):(1~5). In step (4), the total mass of active mineral silicon source and active mineral aluminum source, the added silicon species, NaOH, template agent, the crystal nucleation liquid obtained in step (1), the solid phase crystal obtained in step (1) and the mass ratio of water are 1: (0.05~0.5): (0.05~0.3): (0~0.15): (0.05~0.15): (0.01~0.10): (4~8).

2. The method for synthesizing highly crystalline zeolite molecular sieves by in-situ crystallization of aluminosilicate minerals according to claim 1, characterized in that, In step (1), the hydrothermal treatment temperature is 40~160℃ and the hydrothermal treatment time is 4~24h.

3. The method for synthesizing highly crystalline zeolite molecular sieves by in-situ crystallization of aluminosilicate minerals according to claim 1, characterized in that, The roasting time in step (2) is 1~3h; the roasting time in step (3) is 1~3h.

4. The method for synthesizing highly crystalline zeolite molecular sieves by in-situ crystallization of aluminosilicate minerals according to claim 1, characterized in that, The added silicon species in step (4) is at least one of silica sol, silica gel, silica fume and water glass; the template agent in step (4) is at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-butylamine, triethylamine and diethylammonium.

5. The method for synthesizing highly crystalline zeolite molecular sieves by in-situ crystallization of aluminosilicate minerals according to claim 1, characterized in that, In step (4), the crystallization temperature is 90~150℃ and the crystallization time is 12~48h.

Images