Mesoporous-microporous SBA-15 / HY molecular sieve and preparation method thereof

Abstract

The invention discloses a mesoporous-microporous SBA-15 / HY molecular sieve and a preparation method thereof.The method comprises the steps that S1, a nonionic surfactant, inorganic acid and water are mixed to be uniform, a silicon source is added into the mixture, a hydrolysis reaction is conducted under the ultrasonic emulsification condition, and a solid hydrolysate and mother liquor are obtained through filtering; s2, uniformly mixing the mother liquor, a nonionic surfactant, inorganic acid and water, adding a silicon source into the mixture, carrying out hydrolysis reaction under an ultrasonic emulsification condition, and filtering to obtain a solid hydrolysate and mother liquor; s3, repeating the step S2 for 5-20 times, combining all obtained solid hydrolyzates, and performing hydrothermal crystallization on the solid hydrolyzates by using mother liquor to obtain a crystallized product; and S4, dissolving the crystallized product in a hydrochloric acid solution, stirring, adding an HY molecular sieve, continuously stirring, filtering, drying, and roasting to obtain the mesoporous-microporous SBA-15 / HY molecular sieve. According to the method, the molecular sieve synthesis efficiency is improved, and the synthesis cost and pollution are reduced.

Description

Technical Field

[0001] The invention relates to a meso-microporous SBA-15 / HY molecular sieve and a preparation method thereof. Background Art

[0002] Molecular sieves are widely used in adsorption, separation, catalysis and other fields due to their unique pore structure, especially in petrochemicals. With the continuous development of molecular sieve catalytic applications, molecular sieves with a single pore can no longer meet the various catalyst preparation needs. HY microporous molecular sieves have strong acidity and small pore size (less than 2nm in diameter). The catalyst with HY molecular sieve as carrier has high chain scission cracking activity, but low aromatic hydrogenation saturation activity. In reactions involving large molecules, the reaction raw materials, such as large molecular reactants in heavy oil, cannot enter the pores. The narrow pore structure in the microporous molecular sieve pores limits the reaction. At the same time, the narrow pore diffusion resistance is large, which affects the rapid diffusion and overflow of the reaction product molecules, easily leading to deep cracking and coking, and even further leading to rapid deactivation of the molecular sieve. Compared with HY microporous molecular sieve materials, mesoporous SBA-15 molecular sieves (diameter 2-50nm) can make up for the limitations of microporous molecular sieves in the diffusion of reactants and reaction products. However, since SBA-15 mesoporous molecular sieves have no acidity, the catalyst with SBA-15 mesoporous molecular sieves as carriers has high aromatic hydrogenation saturation activity and low ring-opening activity, which also limits its application in the field of hydrocracking catalysis. The ideal porous material used in the field of hydrocracking should have suitable acidity, excellent shape selectivity and hydrothermal stability on the one hand, and good diffusion performance on the other hand. Obviously, single HY microporous and mesoporous SBA-15 molecular sieve materials cannot meet the above performance. Summary of the invention

[0003] The present invention is made in order to improve the structure, activity, shape selectivity, hydrothermal stability and diffusion performance of molecular sieves, to increase the synthesis efficiency of molecular sieves, and to reduce synthesis costs and pollution.

[0004] As a first aspect of the present invention, it relates to a method for preparing a meso-microporous SBA-15 / HY molecular sieve, the method comprising:

[0005] S1: uniformly mix a nonionic surfactant, an inorganic acid and water, then add silicon source to carry out hydrolysis reaction under ultrasonic emulsification conditions, and filter to obtain a solid hydrolysis product and a mother liquor;

[0006] S2: uniformly mixing the mother liquor, nonionic surfactant, inorganic acid and water, adding silicon source to carry out hydrolysis reaction under ultrasonic emulsification conditions, and filtering to obtain solid hydrolysis product and mother liquor;

[0007] S3 repeats S2 5 to 20 times, combines all the solid hydrolyzed products obtained, and hydrothermally crystallizes the combined solids with the mother liquor to obtain a crystallized product;

[0008] S4: dissolving the crystallized product in a hydrochloric acid solution and stirring, adding HY molecular sieve and continuing stirring, filtering, drying and calcining to obtain the meso-microporous SBA-15 / HY molecular sieve.

[0009] Furthermore, the method specifically comprises:

[0010] S1: nonionic surfactant P123, inorganic acid and water are mixed, stirred at 20-40°C, and then silicon source is added to carry out hydrolysis reaction at 30-60°C under ultrasonic emulsification conditions for 4-16 hours, and solid hydrolysis product and mother liquor are obtained after filtration;

[0011] S2 adds the mother liquor into the reactor, and then adds 20-70% P123, 10-60% inorganic acid and 10-40% water based on the amount of P123, inorganic acid and water added in S1, stirring at 20-30°C, and then adds silicon source at 30-60°C for hydrolysis reaction under ultrasonic emulsification conditions, and obtains solid hydrolysis product and mother liquor after filtration;

[0012] S3 repeats S2 for 5 to 20 times, combines all the solid hydrolyzates obtained, and hydrothermally crystallizes the combined solid hydrolyzates with a small amount of mother liquor to obtain a crystallized product;

[0013] S4 Under room temperature conditions, the crystallized product is dissolved in hydrochloric acid solution, stirred for 8 to 16 hours, and then HY molecular sieve is added. After stirring for 4 to 6 hours, the mesoporous SBA-15 / HY molecular sieve is obtained after filtering, drying and calcining.

[0014] Furthermore, the molar ratio of P123 to water in S1 is 1:5000 to 35000.

[0015] Furthermore, the molar ratio of the inorganic acid to water in S1 is 1:15-75.

[0016] Furthermore, the molar ratio of the silicon source in S1 to P123 is 1:0.01-0.02.

[0017] Furthermore, the mass ratio of the mother liquor to the solid hydrolyzate in S3 is 1 to 50:1.

[0018] Furthermore, the crystallization temperature in S3 is 100-120° C., and the crystallization time is 8-24 hours.

[0019] Furthermore, the crystallization temperature in S4 is 80-100°C.

[0020] Furthermore, the calcination temperature in S4 is 500-600° C., and the calcination time is 4-8 hours.

[0021] Furthermore, the silicon source is one of methyl orthosilicate, ethyl orthosilicate, butyl orthosilicate, silica sol and water glass.

[0022] Furthermore, the inorganic acid is one of hydrochloric acid, phosphoric acid, nitric acid and carbonic acid.

[0023] As a second aspect of the present invention, it relates to a meso-microporous SBA-15 / HY molecular sieve prepared by the above method, wherein the meso-microporous SBA-15 / HY molecular sieve has a grain size of 150-300 nm and a specific surface area of ​​510-550 m 2 / g, the pore volume is 0.60~0.75ml / g, the pore size distribution is 7.5~8.5nm, and the total acid content is 0.18~0.28mmol / g.

[0024] The present invention is to prepare meso-microporous SBA-15 / HY molecular sieve under ultrasonic radiation emulsification, so that the molecular sieve fits more evenly, thereby making the molecular sieve grain size smaller, the particle size uniform and regular, and the specific surface area, pore volume and pore size distribution range more concentrated. The molecular sieve grain size is 150-300nm, compared with the nanoscale (5-50nm) small-grain molecular sieve, the hydrothermal stability is better and it is not easy to agglomerate; relative to the molecular sieve of conventional size (1000-2000nm), the specific surface area of ​​the meso-microporous SBA-15 / HY molecular sieve provided in this case is increased, and the catalyst prepared using it can expose more acidic centers, increase the accessible probability of reactants and catalysts, and thus improve the cracking activity of the catalyst. The specific surface area, pore volume and pore size of the catalyst are relatively concentrated, which can improve the selectivity of the catalyst target product. The present invention combines multiple batches of SBA-15 molecular sieve hydrolyzate without increasing equipment investment, and improves the production efficiency of SBA-15 / HY meso-microporous molecular sieve by increasing the solid / liquid ratio during crystallization, and the more synthesis batches, the more the production efficiency is improved. In addition, the present invention recycles the SBA-15 molecular sieve mother liquor, fully utilizes the inorganic acid and surfactant P123 in the mother liquor, reduces waste discharge, reduces pollution to the environment, and further reduces the cost of raw materials.

[0025] The meso-microporous SBA-15 / HY molecular sieve provided by the present invention is compositely prepared by directional design of HY molecular sieve with small pore size and strong acidity and mesoporous SBA-15 molecular sieve with large pore size and no acidity, giving full play to the respective advantages of SBA-15 mesoporous molecular sieve and HY microporous molecular sieve, making up for the structural and property defects of single-channel porous materials, so that SBA-15 and HY molecular sieves form complementary advantages and synergistic effects in acidity and pore structure, so that the catalyst with meso-microporous SBA-15 / HY molecular sieve as carrier has better aromatic hydrogenation saturation performance and ring-opening activity. The meso-microporous SBA-15 / HY molecular sieve broadens the application range of SBA-15 mesoporous molecular sieve and HY microporous molecular sieve; solves the problem that SBA-15 mesoporous molecular sieve has no acidity and cannot be directly used in catalytic reaction processes such as hydrocracking or hydromodification; and also solves the technical problem that HY microporous molecular sieve has a small pore size and cannot be directly applied to macromolecular reaction processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the XRD spectrum of SBA-15 / HY meso-microporous molecular sieve in Example 2 of the present invention;

[0027] Figure 2 is a low temperature N2 adsorption-desorption isotherm diagram of the SBA-15 / HY meso-microporous molecular sieve in Example 2 of the present invention;

[0028] Figure 3 is the pore distribution curve of SBA-15 / HY meso-microporous molecular sieve in Example 2 of the present invention;

[0029] Figure 4 This is a TEM image of the SBA-15 / HY meso-microporous molecular sieve in Example 2 of the present invention. DETAILED DESCRIPTION

[0030] The following is a detailed description of the embodiments of the present invention: The embodiments of the present invention are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and processes are given, but the protection scope of the present invention is not limited to the following embodiments. The process parameters for which specific conditions are not specified in the following embodiments are generally based on conventional conditions.

[0031] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0032] The inventors implemented relevant technical solutions to synthesize SBA-15 mesoporous molecular sieve with reference to patent CN201911353958.8, patent CN201911353957.3, document Science, 1998, 279, 548, document Micropor. Mesopor. Mater., 2010, 131, 385, document Micropor. Mesopor. Mater., 2010, 131, 385, and document J. Mater. Chem., 2005, 15, 5049. However, these methods only improve a certain problem existing in the synthesis of SBA-15 mesoporous molecular sieves, and cannot effectively solve the current problems of low synthesis efficiency, high cost, serious pollution and single pore structure in the synthesis of SBA-15 molecular sieves. The inventors scaled up these methods and implemented large-scale production, and found that they all had the following three problems: (1) Low single-pot output: The solid-liquid ratio during the synthesis of SBA-15 molecular sieve is low, resulting in low single-pot output; (2) Long synthesis cycle: It takes about 3 to 5 days to complete a synthesis cycle of SBA-15 molecular sieve. The synthesis steps include dissolving the template P123, hydrolyzing TEOS, hydrothermal crystallization and centrifugal roasting; (3) The mother liquor cannot be recycled: A large amount of P123 and hydrochloric acid in the mother liquor are discarded, resulting in waste of resources and environmental pollution.

[0033] Based on this, the inventor made the present invention after further research and development.

[0034] The raw materials used in the embodiments of the present invention include:

[0035] Ethyl orthosilicate (purity 99%, Shandong Polymer Materials Co., Ltd.); silica sol (industrial grade, Guangzhou Chemical Co., Ltd.); nitric acid (1.043 mol / L, Tianjin Komiou Chemical Reagent Co., Ltd.); hydrochloric acid (1.024 mol / L, Tianjin Komiou Chemical Reagent Co., Ltd.).

[0036] The equipment and analysis method used in the embodiments of the present invention include:

[0037] X-ray diffraction (XRD): XRD test of samples was carried out on Rigaku D / max-2500pc X-ray diffractometer, Japan, using Cu Kα ray (λ = 0.1541841nm) as light source, voltage 40KV, current 200mA;

[0038] Pore ​​structure analysis (BET): The specific surface area and pore structure of the sample were measured using the ASAP2405M specific surface and porosity analyzer from Micromeritics Instruments. The measurement conditions are as follows: the sample was purified under a vacuum degree of <104 mtorr. The adsorption volume of N2 on the sample surface at different pressures was measured at liquid nitrogen temperature, and the specific surface area of ​​the sample was calculated using the BET formula; the pore distribution was measured using the BJH method;

[0039] Programmed temperature desorption (NH3-TPD): The acidity was characterized by the NH3-TPD method. Weigh 0.2 g of the sample, purify it with He gas flow at 600 °C for 1 h, cool it to room temperature, adsorb NH3 for 10 min, and purge it with He gas flow for 30 min. Then, continue to purge from room temperature to 100 °C at 10 °C / min until the baseline is stable, then increase to 600 °C at 10 °C / min and maintain for 30 min.

[0040] Transmission electron microscopy (TEM): Transmission electron microscopy (TEM) characterization was carried out on a Tecnai G2 F20 field emission transmission electron microscope (Philips, The Netherlands).

[0041] Example 1

[0042] S1 Take 236g of P123 and add it to 10L of 1.6M hydrochloric acid solution. Heat it to 40℃ and stir it at constant temperature for 6 hours. After P123 is completely dissolved, add 446g of silica sol. Hydrolyze it at constant temperature for 10 hours under ultrasonic emulsification conditions of ultrasonic frequency 40KHz and power 500W. Use Buchner funnel for centrifugal separation and filtration to obtain solid hydrolysis product and mother liquor.

[0043] S2 added 4L 1.6M hydrochloric acid solution and 128g non-ionic surfactant P123 to the mother liquor, stirred at a constant temperature of 40°C for 6h, then added 236g silica sol, and hydrolyzed at a constant temperature of 45°C for 10h under ultrasonic emulsification conditions of ultrasonic frequency of 40KHz and power of 500W. The solid hydrolyzate and mother liquor were obtained by centrifugal separation and filtration using a Buchner funnel.

[0044] S3 repeats the above S2 for 5 times. After the last hydrolysis is completed, add the 6 hydrolysis products separated above to the final mother liquor, raise the temperature to 100°C for hydrothermal crystallization for 16 hours, and filter and wash the crystallized product.

[0045] S4: Dissolve the crystallized product obtained above in 10L 1.8M hydrochloric acid solution at room temperature, stir for 8h, then add 1225g HY molecular sieve and continue stirring for 8h until the two are evenly mixed. Filter, dry at 120℃ for 4h, and calcine at 550℃ for 4h to obtain SBA-15 / HY meso-microporous molecular sieve I.

[0046] The SBA-15 / HY meso-microporous molecular sieve I prepared in this example was subjected to X-ray diffraction (XRD) test, pore structure analysis (BET), programmed temperature desorption (NH3-TPD), and transmission electron microscopy (TEM) characterization, and its properties were measured as shown in Table 1.

[0047] Example 2

[0048] S1: Take 224g of P123 and add it to 10L of 1.8M nitric acid solution. Heat it to 40°C and stir it at constant temperature for 6 hours. After P123 is completely dissolved, add 480g of ethyl orthosilicate. Hydrolyze it at constant temperature for 10 hours under ultrasonic emulsification conditions of ultrasonic frequency 40KHz and power 500W. Use Buchner funnel for centrifugal separation and filtration to obtain solid hydrolysis product and mother liquor.

[0049] S2: add 4L 1.8M nitric acid solution and 118g nonionic surfactant P123 to the mother liquor, stir at constant temperature at 40°C for 6h, add 240g ethyl orthosilicate, and hydrolyze at 40°C for 10h under ultrasonic emulsification conditions of ultrasonic frequency of 40KHz and power of 500W, and centrifuge and filter with a Buchner funnel to obtain a solid hydrolyzate and a mother liquor;

[0050] S3 repeats the above S2 for 10 times. After the last hydrolysis is completed, the 11th hydrolysis product separated previously is added to the final mother liquor, and the temperature is raised to 100° C. for hydrothermal crystallization for 16 hours; the crystallized product is filtered and washed.

[0051] S4: Dissolve the above crystallized product in 10L 1.8M hydrochloric acid solution at room temperature, stir for 8h, then add 2820g HY molecular sieve and continue stirring for 8h until the two are evenly mixed. Filter, dry at 120℃ for 4h, and calcine at 550℃ for 6h to obtain SBA-15 / HY meso-microporous molecular sieve II.

[0052] The SBA-15 / HY meso-microporous molecular sieve II prepared in this example was subjected to X-ray diffraction (XRD) test, pore structure analysis (BET), programmed temperature desorption (NH3-TPD), and transmission electron microscopy (TEM) characterization, and its XRD spectrum was measured as follows: Figure 1 As shown in the figure, the N2 adsorption-desorption isotherm is as follows Figure 2 As shown, the pore distribution curve is as Figure 3 As shown, TEM photos are Figure 4 Its properties are shown in Table 1.

[0053] Example 3

[0054] S1 Take 253g P123 and add it to 10L 2.0M nitric acid solution. Heat it to 40℃ and stir it at constant temperature for 6 hours. After P123 is completely dissolved, add 450g silica sol. Hydrolyze it at constant temperature for 10 hours under ultrasonic emulsification conditions with ultrasonic frequency of 40KHz and power of 500W. Use Buchner funnel for centrifugal separation and filtration to obtain solid hydrolysis product and mother liquor.

[0055] S2: add 4L 2.0M nitric acid solution and 200g non-ionic surfactant P123 to the mother liquor, stir at constant temperature at 40°C for 6h, add 236g silica sol, hydrolyze at constant temperature at 40°C for 10h under ultrasonic emulsification conditions of ultrasonic frequency 40KHz and power 500W, centrifuge and filter with Buchner funnel to obtain solid hydrolyzate and mother liquor;

[0056] S3 repeats the above S2 for 15 times. After the last hydrolysis is completed, the 16 hydrolysis products separated above are added to the final mother liquor, and the temperature is raised to 100° C. for hydrothermal crystallization for 16 hours; the crystallized product is filtered and washed.

[0057] S4: Under normal temperature, the crystallized product obtained above was dissolved in 10L 1.8M hydrochloric acid solution, stirred for 8h, and then 4250g HY molecular sieve was added and stirred for 8h until the two were evenly mixed. Filter, dry at 120℃ for 4h, and calcine at 550℃ for 4h to obtain meso-microporous SBA-15 / HY molecular sieve III.

[0058] The meso-microporous SBA-15 / HY molecular sieve III prepared in this example was subjected to X-ray diffraction (XRD) test, pore structure analysis (BET), programmed temperature desorption (NH3-TPD), and transmission electron microscopy (TEM) characterization, and its properties were measured as shown in Table 1.

[0059] Example 4

[0060] S1 Take 248g P123 and add it to 10L 1.5M carbonate solution. Heat it to 40°C and stir it at constant temperature for 6 hours. After P123 is completely dissolved, add 486g water glass. Hydrolyze it at constant temperature for 10 hours under ultrasonic emulsification conditions of ultrasonic frequency 40KHz and power 500W. Use Buchner funnel for centrifugal separation and filtration to obtain solid hydrolysis product and mother liquor.

[0061] S2: add 4L 1.5M carbonic acid solution and 200g non-ionic surfactant P123 to the mother liquor, stir at constant temperature at 40°C for 6h, add 248g water glass, hydrolyze at constant temperature at 40°C for 10h under ultrasonic emulsification conditions of ultrasonic frequency 40KHz and power 500W, centrifuge and filter with Buchner funnel to obtain solid hydrolyzate and mother liquor;

[0062] S3 repeats the above S2 for 20 times. After the last hydrolysis is completed, the 21st hydrolysis products separated above are added to the final mother liquor, and the temperature is raised to 100° C. for hydrothermal crystallization for 16 hours; the crystallized product is filtered and washed.

[0063] S4: Under normal temperature, the crystallized product obtained above was dissolved in 10L 1.8M nitric acid solution, stirred for 8h, and then 5530g HY molecular sieve was added and stirred for 8h until the two were evenly mixed. Filter, dry at 120℃ for 4h, and calcine at 550℃ for 4h to obtain meso-microporous SBA-15 / HY molecular sieve IV.

[0064] The meso-microporous SBA-15 / HY molecular sieve IV prepared in this embodiment was subjected to X-ray diffraction (XRD) test, pore structure analysis (BET), programmed temperature desorption (NH3-TPD), and transmission electron microscopy (TEM) characterization, and its properties were measured as shown in Table 1.

[0065] Example 5

[0066] S1 Take 236g of P123 and add it to 10L of 2.1M nitric acid solution. Heat it to 40°C and stir it at constant temperature for 6 hours. After P123 is completely dissolved, add 448g of silica sol. Hydrolyze it at constant temperature for 10 hours under ultrasonic emulsification conditions of ultrasonic frequency 40KHz and power 500W. Use Buchner funnel for centrifugal separation and filtration to obtain solid hydrolysis product and mother liquor.

[0067] S2: add 4L 2.1M nitric acid solution and 200g non-ionic surfactant P123 to the mother liquor, stir at constant temperature at 40°C for 6h, add 232g silica sol, hydrolyze at constant temperature at 40°C for 10h under ultrasonic emulsification conditions of ultrasonic frequency of 40KHz and power of 500W, centrifuge and filter with a Buchner funnel to obtain a solid hydrolyzate and a mother liquor;

[0068] S3 repeats the above S2 for 8 times. After the last hydrolysis is completed, add the 9 hydrolysis products separated previously to the final mother liquor, raise the temperature to 100°C for hydrothermal crystallization for 16 hours; filter and wash the crystallized product.

[0069] S4: Under normal temperature, the crystallized product obtained above was dissolved in 10L 2.0M hydrochloric acid solution, stirred for 8h, and then 2395g HY molecular sieve was added and stirred for 8h until the two were evenly mixed. Filtered, dried at 120℃ for 4h, and calcined at 550℃ for 4h to obtain meso-microporous SBA-15 / HY molecular sieve V.

[0070] The meso-microporous SBA-15 / HY molecular sieve V prepared in this embodiment was subjected to X-ray diffraction (XRD) test, pore structure analysis (BET), programmed temperature desorption (NH3-TPD), scanning electron microscopy (SEM) characterization, and transmission electron microscopy (TEM) characterization, and its properties were measured as shown in Table 1.

[0071] Table 1 Properties of meso-microporous SBA-15 / HY molecular sieves prepared in Examples 1 to 5

[0072]

[0073]

[0074] As shown in Table 1, the meso-microporous SBA-15 / HY molecular sieve prepared by the method of the present invention has a grain size of 150-300 nm and a specific surface area of ​​510-550 m 2 / g, pore volume is 0.60-0.75ml / g, pore size distribution is 7.5-8.5nm, total acid content is 0.18-0.28mmol / g, so it can be directly used in catalytic reaction processes such as hydrocracking or hydromodification, and can be directly applied to macromolecular reaction processes, broadening the application range of meso-microporous SBA-15 / HY molecular sieve.

[0075] Although the specific embodiments of the present invention have been described in detail, it will be understood by those skilled in the art. According to all the teachings disclosed, various modifications and replacements can be made to those details, and these changes are all within the protection scope of the present invention. The full scope of the present invention is given by the attached claims and any equivalents thereof.

Claims

1. A method for preparing meso-microporous SBA-15 / HY molecular sieve, characterized in that: The method comprises: S1: uniformly mixing a nonionic surfactant, an inorganic acid and water, adding silicon source thereto, performing hydrolysis reaction under ultrasonic emulsification conditions, and filtering to obtain a solid hydrolysis product and a mother liquor; S2: uniformly mixing the mother liquor, nonionic surfactant, inorganic acid and water, adding silicon source thereto to carry out hydrolysis reaction under ultrasonic emulsification conditions, and filtering to obtain solid hydrolysis product and mother liquor; S3 repeats S2 5 to 20 times, combines all the solid hydrolyzed products obtained, and hydrothermally crystallizes them with the mother liquor to obtain a crystallized product; S4: dissolving the crystallized product in a hydrochloric acid solution and stirring, adding HY molecular sieve and continuing stirring, filtering, drying and calcining to obtain the meso-microporous SBA-15 / HY molecular sieve.

2. The method according to claim 1, characterized in that The method specifically comprises: S1: nonionic surfactant P123, inorganic acid and water are mixed, stirred at 20-40°C, and then silicon source is added to carry out hydrolysis reaction at 30-60°C under ultrasonic emulsification conditions for 4-16 hours, and solid hydrolysis product and mother liquor are obtained after filtration; S2 adds the mother liquor into the reactor, and then adds 20-70% P123, 10-60% inorganic acid and 10-40% water based on the amount of P123, inorganic acid and water added in S1, stirring at 20-30°C, and then adds silicon source to carry out hydrolysis reaction at 30-60°C under ultrasonic emulsification conditions, and obtains solid hydrolysis product and mother liquor after filtering; S3 repeats S2 for 5 to 20 times, combines all the solid hydrolyzates obtained, and hydrothermally crystallizes the combined solid hydrolyzates with a small amount of mother liquor to obtain a crystallized product; S4 Under room temperature conditions, the crystallized product is dissolved in hydrochloric acid solution, stirred for 8 to 16 hours, and then HY molecular sieve is added. After stirring for 4 to 6 hours, the mesoporous SBA-15 / HY molecular sieve is obtained after filtering, drying and calcining.

3. The method according to claim 2, characterized in that The molar ratio of P123 to water in S1 is 1:5000-35000.

4. The method according to claim 2, characterized in that The molar ratio of the inorganic acid to water in S1 is 1:15-75.

5. The method according to claim 2, characterized in that The molar ratio of the silicon source in S1 to P123 is 1:0.01-0.

02.

6. The method according to claim 2, characterized in that The mass ratio of the mother liquor to the solid hydrolyzate in S3 is 1 to 50:

1.

7. The method according to claim 2, characterized in that The crystallization temperature in S3 is 100-120° C., and the crystallization time is 8-24 hours.

8. The method according to claim 7, characterized in that The crystallization temperature in S4 is 80-100°C.

9. The method according to claim 2, characterized in that The calcination temperature in S4 is 500-600° C., and the calcination time is 4-8 hours.

10. The method according to claim 2, characterized in that The silicon source is one of methyl orthosilicate, ethyl orthosilicate, butyl orthosilicate, silica sol and water glass.

11. The method according to claim 2, characterized in that The inorganic acid is one of hydrochloric acid, phosphoric acid, nitric acid and carbonic acid.

12. The meso-microporous SBA-15 / HY molecular sieve prepared by the method according to any one of claims 1 to 11, characterized in that: The crystal size of the meso-microporous SBA-15 / HY molecular sieve is 150-300 nm, and the specific surface area is 510-550 m 2 / g, the pore volume is 0.60~0.75ml / g, the pore size distribution is 7.5~8.5nm, and the total acid content is 0.18~0.28mmol / g.

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