Inverse opal ssz-13 molecular sieve and method of synthesis thereof

Abstract

The present application relates to a kind of inverse opal SSZ-13 molecular sieve and its synthesis method and application.Firstly, 3-amino phenol, ethanol, formaldehyde solution, ammonia and other raw materials are used to synthesize phenolic resin microspheres, then carbonized by calcining at high temperature under protective atmosphere to obtain carbon spheres;Then, isopropyl alcohol aluminum or sodium metaaluminate, tetraethyl orthosilicate or fumed silica, water, ammonium chloride, N, N, N-trimethyl-1-adamantyl ammonium hydroxide or benzyl trimethyl ammonium is prepared into precursor solution, the precursor solution is mixed with carbon spheres uniformly, then aging, crystallization, high temperature calcination treatment in turn, to obtain the SSZ-13 molecular sieve with inverse opal structure;Finally, the prepared molecular sieve is mixed with ammonium nitrate solution for ammonium exchange treatment, after solid-liquid separation, high temperature calcination under protective atmosphere again, the SSZ-13 molecular sieve prepared by this method has the advantages of large specific surface area, three-dimensional ordered pore structure, etc., reactants and products can diffuse freely in the pore, and can be used for MTO catalytic reaction and has long catalytic life.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new materials and catalysts, in particular to a SSZ-13 molecular sieve with inverse opal structure and a synthesis method thereof. BACKGROUND

[0002] SSZ-13 molecular sieve is a kind of small-pore molecular sieve with CHA structure, and its pore size is 0.38 nm. Its unique composition and structure make it not only applicable to MTO reaction to obtain a high proportion of light olefins, but also applicable to loading of metal Cu to prepare Cu-based SSZ-13 molecular sieve for denitration field, thereby achieving high research significance and economic value. In addition, the SSZ-13 molecular sieve membrane can also be applied to the separation of methane / carbon dioxide. In summary, such a large number of applications make it very important to develop the SSZ-13 molecular sieve in depth.

[0003] Although the unique structure of the SSZ-13 molecular sieve makes it have excellent product selectivity, it also brings problems such as limited diffusion of reactants and products, and the key to solving the problems lies in changing the synthesis process of the molecular sieve and then introducing additional mesopores and macropores. The synthesis path of hierarchical pore molecular sieve at the present stage is mainly divided into structure destruction method and structure construction method. The structure destruction method includes dealumination, desilication and other methods, which generally cause great damage to the framework, for example, dealumination is at the expense of the acid center of the molecular sieve, which will affect the catalytic performance of the molecular sieve to some extent. The structure construction method mainly includes soft template method and hard template method, which almost have no effect on the framework and crystallinity of the molecular sieve. The central idea of the soft template method is the template mechanism, that is, using cationic polymer, cationic surfactant molecules and organic silane macromolecules as template agents, using the micelles of the supermolecular structure formed by the template agents in the solution as templates, and through the sol-gel process under the interaction of organic and inorganic species, a porous material with narrow pore size distribution and regular ordered pore structure is self-assembled. For example, the literature (ACS Catalysis 2016, 6, (4): 2163-2177) reports a kind of double quaternary ammonium salt surfactant (C22-4-4Br2) as a mesopore agent for synthesis of molecular sieve. The double quaternary ammonium salt has a hydrophilic group at one end, which has a strong interaction with the molecular sieve framework, and a long carbon chain as a hydrophobic group at the other end, which is used to inhibit the growth of the molecular sieve crystal, thereby preparing a SSZ-13 molecular sieve with micro-mesoporous multi-level pores. The mesopores of the molecular sieve prepared by this method have poor connectivity and adjustability, and cannot accurately control the pore, which still produces great resistance to the diffusion of reactants and products.

[0004] Hard template method is a very common and general method for preparing hierarchical pore molecular sieves at present. In this method, a hard template is usually added in the synthesis system of microporous molecular sieves, and the existing ordered pore structure in the template is utilized to crystallize for a period of time at a certain temperature, and finally the solid hard template is removed to obtain hierarchical pore molecular sieve materials with complementary structure. Previously, our research group successfully introduced macroporous and mesoporous channels into ZSM-5 molecular sieve single crystals for the first time by using the hard template method and the dry gel method, and thus the ordered macroporous-mesoporous hierarchical pore silicon-aluminum molecular sieve ZSM-5 single crystal has both hierarchical pore channel structure and single crystal structure (see CN106283187B). Subsequently, we also prepared a series of SAPO-34 molecular sieve single crystals (see CN2025102015048, CN2025102015086), SSZ-13 molecular sieves (see CN2024119663109) and the like with different structures and properties by using carbon templates. On the basis of the above research results, we have newly developed a SSZ-13 molecular sieve with inverse opal structure, which further enriches the product system of molecular sieve catalysts. SUMMARY

[0005] One of the purposes of the present application is to provide a preparation method of a SSZ-13 molecular sieve with inverse opal structure, comprising: carbonizing phenolic resin microspheres at high temperature to obtain carbon spheres; preparing a precursor solution by using an aluminum source, a structure directing agent, ammonium chloride, a silicon source and water, mixing the precursor solution with the carbon spheres to obtain a dry gel; and subjecting the dry gel to crystallization and high-temperature calcination treatment to obtain the inverse opal SSZ-13 molecular sieve.

[0006] Further, the preparation method of the carbon spheres is as follows: uniformly mixing 3-amino phenol with water, and then sequentially adding an alcohol solvent, a formaldehyde aqueous solution and an ammonia solution to obtain a mixture, heating the mixture to 20-40℃ for 4-12h, and then heating the mixture to 80-100℃ for 12-24h in a closed state, subjecting the mixture to solid-liquid separation, heating the obtained solid to 600-700℃ under a protective atmosphere for high-temperature carbonization, and finally naturally cooling to obtain carbon spheres with a particle size of 300-400nm.

[0007] Further, the amount ratio of 3-amino phenol, water, alcohol solvent, formaldehyde aqueous solution and ammonia solution required for the reaction is 3-4g:200-300mL:90-200mL:2-3g:2-3g, wherein the concentration of the formaldehyde aqueous solution is 30wt%-40wt%, and the concentration of the ammonia solution is 40wt%-45wt%.

[0008] Further, the aluminum source is selected from at least one of aluminum isopropoxide and sodium metaaluminate.

[0009] Further, the structure directing agent is selected from at least one of N,N,N-trimethyl-1-adamantylammonium hydroxide and benzyltrimethylammonium.

[0010] Further, the silicon source is selected from at least one of tetraethyl orthosilicate and fumed silica.

[0011] Further, the mass ratio of the aluminum source, the structure-directing agent, the ammonium chloride and the silicon source required for the reaction is 0.2-0.7:5-10:0.2-0.3:3-13.

[0012] Further, the mass ratio of the precursor solution and the carbon spheres when mixed is 1:8-12.

[0013] Further, the aging temperature is 70-90 DEG C, and the aging time is 24h or more.

[0014] Further, the crystallization temperature is 150-170 DEG C, and the crystallization time is 4d or more.

[0015] Further, the high-temperature calcination atmosphere is air, the heating rate is 1-5 DEG C / min, the calcination temperature is 590-610 DEG C, and the calcination time is 5-9h.

[0016] Further, the molecular sieve after high-temperature calcination also needs to be subjected to ammonium exchange treatment, and the specific process is as follows: the molecular sieve after high-temperature calcination is mixed with an ammonium nitrate solution in a mass ratio of 1:5-15, the obtained mixture is heated to 70-90 DEG C for ammonium exchange, after solid-liquid separation, the solid is heated to 90-110 DEG C for full drying; after repeating the ammonium exchange-drying multiple times, the molecular sieve is heated to 500-600 DEG C at a heating rate of 1-5 DEG C / min in an air atmosphere for calcination for 5-9h, and after cooling, the H-type inverse opal SSZ-13 molecular sieve is obtained.

[0017] The second object of the present application is to provide an inverse opal SSZ-13 molecular sieve prepared by the above method.

[0018] The present application uses the carbon spheres formed after carbonization of phenolic resin as a sacrificial template, and forms three-dimensional ordered inverse opal structure channels in the SSZ-13 molecular sieve crystal, thereby solving the problems of limited diffusion of reactants and products and the problems of disordered channel distribution and poor channel adjustability of the channels formed by the traditional soft template method, and converting the Na-type molecular sieve into an H-type molecular sieve by means of ammonium exchange, so that the molecular sieve can be better applied in MTO reactions.

[0019] Compared with the prior similar products or technologies, the progress effect of the present application is embodied in the following aspects:

[0020] (1) The carbon template originally used for synthesizing SAPO-34 molecular sieve is innovatively used for synthesizing SSZ-13 molecular sieve, which expands the application range of the carbon template and enriches the types of molecular sieve products, thereby providing more choices for the market;

[0021] (2) The pore structure of the SSZ-13 molecular sieve prepared by using the carbon sphere as a hard template is more stable, and has hierarchical pores and inverse opal structure, so that the specific surface area is larger and the catalytic life is longer, and the SSZ-13 molecular sieve has good application prospects in many fields such as catalysis and separation;

[0022] (3) The Na-type molecular sieve has no activity in the MTO reaction, and is converted into the H-type molecular sieve through ammonium exchange treatment, and then can be applied to the MTO reaction.

[0023] (4) The preparation process is simple and easy to realize, and can be mass-produced, which is helpful for the practical application of the molecular sieve product. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The SEM photo of the SSZ-13 molecular sieve prepared in Example 1.

[0025] Figure 2 The SEM photo of the microporous molecular sieve sample prepared in Comparative Example 1. DETAILED DESCRIPTION

[0026] In order for those skilled in the art to fully understand the technical solutions and beneficial effects of the present application, the following will be further described in detail in combination with specific embodiments and drawings. It should be emphasized that the following examples are only preferred embodiments of the present application, and any simple improvement and replacement made on this basis shall fall within the protection scope of the present application.

[0027] Example 1

[0028] (1) Preparation of carbon sphere

[0029] 3.632g of 3-aminophenol was added to 240mL of deionized water, followed by 96mL of anhydrous ethanol and stirring to be uniform, and then 2.672g of formaldehyde aqueous solution (concentration 40wt%) and 2.248g of ammonia water (concentration 40wt%) were added and stirred to be uniform, and the obtained mixture was stirred at 30℃ for 5h and then transferred to a reaction kettle, and the reaction kettle was sealed and placed at 80℃ for crosslinking reaction. After the reaction was completed, centrifugal separation was performed to obtain phenolic resin microspheres with a particle size of about 600nm. The phenolic resin microspheres were heated to 650℃ under N2 protection atmosphere, and carbonized for 7h, and then naturally cooled to obtain carbon spheres with a particle size of about 400nm.

[0030] (2) Synthesis of SSZ-13 molecular sieve

[0031] Into a beaker, 0.615 g aluminum isopropoxide, 20.37 g N,N,N-trimethyl-1- adamantylammonium hydroxide aqueous solution with a concentration of 25 wt%, 11.77 g deionized water, 0.246 g ammonium chloride were added, stirred until the aluminum isopropoxide was completely hydrolyzed, then 12.5 g tetraethyl silicate was added and stirring was continued for 4 h to obtain a precursor solution.

[0032] Into 1 g of the carbon spheres, 0.1 g of the precursor solution was added dropwise, and the obtained mixture was transferred into an oven and aged at 80℃ for 24 h, so that the precursor solution entered the gap between the carbon spheres and formed a xerogel.

[0033] The xerogel was placed in a reaction kettle and crystallized at 160℃ for 5 d. Finally, the crystallized solid sample was transferred into a muffle furnace and heated to 600℃ at a heating rate of 2℃ / min in an air atmosphere for calcination for 7 h to remove the carbon spheres and the structure directing agent, and the furnace was cooled to room temperature to obtain inverse opal SSZ-13 molecular sieves.

[0034] 1 g of the inverse opal SSZ-13 molecular sieves was mixed with 10 g of an ammonium nitrate solution with a concentration of 1 mol / L, and the obtained mixture was heated to 80℃ for ammonium exchange for 2 h, followed by suction filtration and drying of the filter residue at 100℃. The ammonium exchange-suction filtration-drying was repeated three times, and then the solid product was heated to 550℃ at a heating rate of 2℃ / min in an air atmosphere for calcination for 7 h, and finally H-type inverse opal SSZ-13 molecular sieves were obtained.

[0035] Example 2

[0036] (1) Preparation of carbon spheres

[0037] Into 240 mL of deionized water, 3.632 g of 3-aminophenol was added, followed by 150 mL of anhydrous ethanol and stirring until uniform, then 2.672 g of formaldehyde aqueous solution (concentration 40 wt%) and 2.248 g of ammonia water (concentration 40 wt%) were added and stirring until uniform, and the obtained mixture was transferred into a reaction kettle after stirring and reacting at 30℃ for 5 h, and the reaction kettle was sealed and placed at 80℃ for crosslinking reaction, and after the reaction was completed, centrifugal separation was performed to obtain phenolic resin microspheres with a particle size of about 500 nm. The phenolic resin microspheres were heated to 650℃ for carbonization for 7 h using N2 as a protective atmosphere, and then naturally cooled to obtain carbon spheres with a particle size of about 350 nm.

[0038] (2) Synthesis of SSZ-13 molecular sieves

[0039] Into a beaker, 0.615 g aluminum isopropoxide, 20.37 g of a 25 wt% aqueous solution of N,N,N-trimethyl-1-adamantylammonium hydroxide, 11.77 g of deionized water, 0.246 g of ammonium chloride were added, stirred until the aluminum isopropoxide was completely hydrolyzed, then 3.6 g of fumed silica was added and stirring was continued for 8 h to obtain a precursor solution.

[0040] Into 1 g of carbon spheres, 0.1 g of the precursor solution was added dropwise, and the resulting mixture was transferred to an oven and aged at 80°C for 24 h to form a xerogel.

[0041] The xerogel was placed in a reaction kettle and crystallized at 160°C for 5 d. Finally, the crystallized solid sample was transferred to a muffle furnace and heated to 600°C at a heating rate of 2°C / min in an air atmosphere and calcined for 7 h, and the furnace was cooled to room temperature to obtain the inverse opal SSZ-13 molecular sieve.

[0042] Example 3

[0043] (1) Preparation of carbon spheres

[0044] Into 240 mL of deionized water, 3.632 g of 3-aminophenol was added, followed by 200 mL of anhydrous ethanol and stirring until uniform, then 2.672 g of an aqueous formaldehyde solution (40 wt% concentration), 2.248 g of ammonia water (40 wt% concentration) were added and stirring was continued until uniform, and the resulting mixture was transferred to a reaction kettle after stirring and reacting at 30°C for 5 h, and the reaction kettle was sealed and placed in a crosslinking reaction at 80°C, and after the reaction was completed, centrifugation was performed to obtain phenolic resin microspheres with a particle size of about 400 nm. Using N2 as a protective atmosphere, the phenolic resin microspheres were heated to 650°C and carbonized for 7 h, and then naturally cooled to obtain carbon spheres with a particle size of 300 nm.

[0045] (2) Synthesis of SSZ-13 molecular sieve

[0046] Into a beaker, 0.246 g of sodium metaaluminate, 20.37 g of a 25 wt% aqueous solution of N,N,N-trimethyl-1-adamantylammonium hydroxide, 11.77 g of deionized water, 0.246 g of ammonium chloride were added, and stirring was performed for 5 min to hydrolyze the sodium metaaluminate, then 12.5 g of tetraethyl orthosilicate was added and stirring was continued for 4 h to obtain a precursor solution.

[0047] Into 1 g of carbon spheres, 0.1 g of the precursor solution was added dropwise, and the resulting mixture was transferred to an oven and aged at 80°C for 24 h to form a xerogel.

[0048] The dry gel was placed in a reactor and crystallized at 160°C for 5d. Finally, the crystallized solid sample was transferred to a muffle furnace and calcined at 600°C for 7h with a heating rate of 2°C / min in air atmosphere, and the reactor was cooled to room temperature to obtain the inverse opal SSZ-13 molecular sieve.

[0049] Example 4

[0050] (1) Preparation of carbon spheres

[0051] 3.632g of 3-aminophenol was added to 240mL of deionized water, followed by 96mL of anhydrous ethanol and stirred until uniform, then 2.672g of formaldehyde aqueous solution (concentration 40wt%) and 2.248g of ammonia water (concentration 40wt%) were added and stirred until uniform. The resulting mixture was stirred at 30°C for 5h and then transferred to a reactor, which was sealed and placed in a 80°C water bath for crosslinking reaction. After the reaction was completed, centrifugal separation was performed to obtain phenolic resin microspheres with a particle size of 600nm. The phenolic resin microspheres were heated to 650°C for carbonization for 7h using N2 as a protective atmosphere, and then naturally cooled to obtain carbon spheres with a particle size of 400nm.

[0052] (2) Synthesis of SSZ-13 molecular sieve

[0053] 0.2g of sodium metaaluminate, 10g of benzyltrimethylammonium, 11.77g of deionized water, and 0.246g of ammonium chloride were added to a beaker and stirred until the sodium metaaluminate was completely hydrolyzed. Then 3g of fumed silica was added and stirred for 4h to obtain a precursor solution.

[0054] 0.1g of the precursor solution was added dropwise to 1g of the carbon spheres, and the resulting mixture was transferred to an oven and aged at 80°C for 24h to form a dry gel.

[0055] The dry gel was then placed in a reactor and crystallized at 160°C for 5d. Finally, the crystallized solid sample was transferred to a muffle furnace and calcined at 600°C for 7h with a heating rate of 2°C / min in air atmosphere, and the reactor was cooled to room temperature to obtain the inverse opal SSZ-13 molecular sieve.

[0056] 1g of the inverse opal SSZ-13 molecular sieve was mixed with 10g of a 1mol / L ammonium nitrate solution, and the resulting mixture was heated to 80°C for 2h for ammonium exchange. Then, the mixture was suction filtered and the filter residue was dried at 100°C. The ammonium exchange-suction filtration-drying process was repeated three times. Then, the solid product was heated to 550°C for calcination for 7h with a heating rate of 2°C / min in air atmosphere, and finally H-type inverse opal SSZ-13 molecular sieve was obtained.

[0057] Comparative Example 1

[0058] 4.227 g of N,N,N-trimethyl-1-adamantyl ammonium hydroxide (25 wt%) was mixed with 9.63 g of deionized water. 0.5106 g of aluminum isopropoxide was added to the resulting N,N,N-trimethyl-1-adamantyl ammonium hydroxide aqueous solution and stirred for 1 h to allow complete hydrolysis. Then, 10 g of As-30 silica sol was added and stirring was continued for 6 h to obtain the precursor solution.

[0059] The precursor solution was transferred to a polytetrafluoroethylene-lined reactor, which was heated to 160°C and held for hydrothermal crystallization for 4 days. After hydrothermal crystallization, the solid product was centrifuged and washed with water until neutral, then transferred to an 80°C oven for overnight drying. The dried solid product was placed in a muffle furnace and calcined at 600°C for 7 hours in air at a heating rate of 2°C / min, followed by furnace cooling to room temperature to obtain microporous SSZ-13 molecular sieve.

[0060] 0.1 g of microporous SSZ-13 molecular sieve was mixed with 10 g of 1 mol / L ammonium nitrate solution. The resulting mixture was heated to 80 °C for ammonium exchange for 2 h, followed by filtration and drying of the filter residue at 100 °C. This ammonium exchange-filtration-drying process was repeated three times. Subsequently, the solid product was heated to 550 °C and calcined in air at a heating rate of 2 °C / min for 7 h to obtain H-type microporous SSZ-13 molecular sieve.

[0061] To fully understand the performance of the SSZ-13 molecular sieves prepared in each embodiment and comparative example, samples were taken and the following tests were conducted:

[0062] (1) SEM testing

[0063] SEM images of the H-type inverse opal SSZ-13 molecular sieve prepared in Example 1 are shown below. Figure 1 As shown in the figure, the molecular sieve sample contains a uniform macroporous structure (pore size of approximately 500 nm), and these macroporous structures constitute an opal structure. Therefore, the molecular sieve has an inverse opal structure, meaning that the inverse opal structure has been successfully introduced into the SSZ-13 molecular sieve.

[0064] SEM images of the H-type microporous SSZ-13 molecular sieve sample prepared in Comparative Example 1 are shown below. Figure 2 As shown in the figure, this molecular sieve is a pure microporous molecular sieve, and no additional pores can be observed in the SEM.

[0065] (2) Specific surface area and pore size distribution test

[0066] The different structure SSZ-13 molecular sieve samples prepared in Example 1 and Comparative Example 1 were characterized by nitrogen physical adsorption (nitrogen isothermal adsorption test), and the equipment model was Micromeritics ASAP 2020 type nitrogen physical adsorption instrument. Before analysis, the samples need to be pretreated, and the pretreatment method is as follows: two kinds of molecular sieve samples were respectively loaded into quartz tubes, then vacuumized and heated to 300℃ at a heating rate of 10℃ / min, and vacuumized for 12h. The pretreated samples were tested for specific surface area and pore size distribution, and the results are shown in Table 1.

[0067] Table 1 Comparison table of pore structure parameters of molecular sieve samples of Example 1 and Comparative Example 1

[0068]

[0069] From Table 1, it can be seen that the introduction of inverse opal structure in Example 1 significantly increases the specific surface area and mesopore volume of the molecular sieve, effectively improving the diffusion flow of the product and the reactant.

[0070] (3) Catalytic performance test

[0071] The H-type inverse opal SSZ-13 molecular sieve sample prepared in Example 1 was pressed into a tablet, and then crushed to 40-60 mesh. 0.1g of molecular sieve particle catalyst was weighed and loaded into a fixed bed reaction device for MTO performance evaluation, and the specific process was as follows: the fixed bed reaction device was activated at 500℃ for 1h under nitrogen, then cooled to 400℃, and nitrogen was used to carry methanol, and the nitrogen flow rate was 15mL / min, and the weight hourly space velocity of methanol was 1h -1 The reaction products were analyzed and detected by gas chromatograph (GC-2014C), and the results are shown in Table 2.

[0072] Table 2 Comparison table of catalytic performance test results of molecular sieve samples of Example 1 and Comparative Example 1

[0073]

[0074] Note: = indicates olefins, + indicates all products with carbon number greater than or equal to 5.

[0075] From Table 2, it can be seen that compared with Comparative Example 1, the H-type inverse opal SSZ-13 molecular sieve in Example 1 has a longer catalytic life, and the product distribution is basically the same as that of the comparative sample.

Claims

1. A method for preparing inverse opal SSZ-13 molecular sieve, characterized in that... The method includes: carbonizing phenolic resin microspheres at high temperature to obtain carbon spheres; preparing a precursor solution using an aluminum source, a structure directing agent, ammonium chloride, a silicon source, and water; mixing and aging the precursor solution with the carbon spheres to obtain a dry gel; and subjecting the dry gel to crystallization and high-temperature calcination to obtain an inverse opal SSZ-13 molecular sieve.

2. The method as described in claim 1, characterized in that... The carbon spheres are prepared as follows: 3-aminophenol is mixed with water until homogeneous, and then alcohol solvent, formaldehyde aqueous solution, and ammonia aqueous solution are added in sequence. The resulting mixture is heated to 20-40℃ and reacted for 4-12 hours. Then, it is heated to 80-100℃ and reacted in a sealed container for 12-24 hours. After solid-liquid separation, the solid is placed under a protective atmosphere and heated to 600-700℃ for high-temperature carbonization. After natural cooling, carbon spheres with a particle size of 300-400 nm are obtained.

3. The method as described in claim 2, characterized in that: The ratio of 3-aminophenol, water, alcohol solvent, formaldehyde aqueous solution, and ammonia aqueous solution is 3-4g:200-300mL:90-200mL:2-3g:2-3g, the concentration of formaldehyde aqueous solution is 30wt%-40wt%, and the concentration of ammonia solution is 40wt%-45wt%.

4. The method as described in claim 1, characterized in that: The aluminum source is selected from at least one of aluminum isopropoxide and sodium aluminate; the structure directing agent is selected from at least one of N,N,N-trimethyl-1-adamantyl ammonium hydroxide and benzyltrimethylammonium; and the silicon source is selected from at least one of tetraethyl silicate and fumed silica.

5. The method as described in claim 1, characterized in that: The mass ratio of aluminum source, structure guiding agent, ammonium chloride, and silicon source is 0.2-0.7:5-10:0.2-0.3:3-13.

6. The method as described in claim 1, characterized in that: The mass ratio of the precursor liquid to the carbon balls is 1:8-12.

7. The method as described in claim 1, characterized in that: The aging temperature is 70-90℃ and the aging time is more than 24 hours. The crystallization temperature is 150-170℃ and the crystallization time is more than 4 days.

8. The method as described in claim 1, characterized in that: The high-temperature calcination atmosphere is air, the heating rate is 1-5℃ / min, the calcination temperature is 590-610℃, and the calcination time is 5-9h.

9. The method as described in claim 1, characterized in that: The molecular sieve after high-temperature calcination still needs to undergo ammonium exchange treatment. The specific process is as follows: the molecular sieve after high-temperature calcination is mixed with ammonium nitrate solution at a mass ratio of 1:5-15. The resulting mixture is heated to 70-90℃ for ammonium exchange. After solid-liquid separation, the solid is heated to 90-110℃ and dried thoroughly. After repeating the ammonium exchange-drying process several times, the molecular sieve is heated to 500-600℃ for 5-9 hours in air at a heating rate of 1-5℃ / min. After cooling, H-type inverse opal SSZ-13 molecular sieve is obtained.

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