Method for rapidly preparing SSZ-13 zeolite membrane through Na2S2O8 auxiliary strategy

Abstract

The invention relates to the technical field of zeolite membrane preparation, in particular to a method for rapidly preparing an SSZ-13 zeolite membrane through a Na2S2O8 auxiliary strategy, and the method is suitable for efficient separation of gas mixtures such as CO2 / CH4 and the like. The invention provides a method for rapidly preparing an SSZ-13 zeolite membrane by using a Na2S2O8 auxiliary strategy and accurately controlling a matching index of a seed crystal size and a carrier aperture within an optimization interval of 0.5-1.0, and solves the problems of long synthesis time, non-uniform membrane quality and difficulty in large-scale production in the prior art.

Description

Technical Field

[0001] This invention relates to the field of zeolite membrane preparation technology, specifically to a method for rapidly preparing SSZ-13 zeolite membranes using a Na2S2O8-assisted strategy, suitable for the efficient separation of gas mixtures such as CO2 / CH4. Background Technology

[0002] With the widespread utilization of natural gas and biogas resources, efficient separation of CO2 and CH4 has become crucial for improving fuel quality and reducing pipeline corrosion. Compared with traditional absorption and cryogenic distillation, membrane separation technology offers advantages such as low energy consumption, compact equipment, and simple operation. Zeolite membranes, due to their regular microporous structure and good thermochemical stability, exhibit excellent performance in gas separation. SSZ-13 zeolite, with a pore size of 0.38 nm, is similar to the kinetic diameters of CO2 and CH4, combining the ability to size-screen and preferentially adsorb CO2, making it an ideal separation material.

[0003] However, the traditional preparation of SSZ-13 zeolite membranes suffers from long crystallization times and poor reproducibility, making it difficult to achieve large-scale production of thin, defect-free membranes with controllable microstructures. While existing technologies disclose strategies such as increasing crystallization temperature, employing the bisammonium method, and using concentrated template agents, these measures narrow the operational synthesis window and complicate industrial-scale production. Therefore, developing a rapid, controllable, and scalable method for preparing SSZ-13 zeolite membranes is of great significance. Summary of the Invention

[0004] The purpose of this invention is to provide a method for rapidly preparing SSZ-13 zeolite membranes using a Na2S2O8-assisted strategy, thereby solving the problems of long synthesis time, uneven membrane quality, and difficulty in scaling up existing technologies.

[0005] This invention provides a method for rapidly preparing SSZ-13 zeolite membranes using a Na2S2O8-assisted strategy, comprising the following steps: (1) Prepare SSZ-13 molecular sieve as seed crystal; (2) Select a carrier with a seed particle size to carrier pore size ratio of 0.5-1, and coat the seed on the carrier surface to form a seeded carrier; (3) Assemble several seed carriers in parallel on a support frame and immerse them as a whole in a casting solution with a molar ratio of 1.0SiO2: 0.001-0.01Al2O3: 0.005-0.04Na2S2O8: 0.1-0.5TMAdaOH: 0.1-0.2Na2O: 20-100H2O. Then immerse the seed carriers in the casting solution for hydrothermal crystallization for 10-36 hours to form a preform film. (4) The embryo membrane is calcined in an ozone atmosphere to remove the template agent, thereby obtaining SSZ-13 zeolite membrane.

[0006] Preferably, the SSZ-13 molecular sieve is formed through a molecular sieve conversion pathway.

[0007] Preferably, the particle size of SSZ-13 molecular sieve is 100-450 nm.

[0008] Preferably, the seed crystals are prepared as a seed crystal suspension of 0.1-2 wt%, and the seed crystals are coated on the surface of the carrier by one or more of the following methods: immersion coating, vacuum coating, and wiping coating.

[0009] Preferably, the carrier is one of sheet type, tubular type, single-channel hollow fiber or multi-channel hollow fiber.

[0010] Preferably, the hydrothermal synthesis temperature is 150-180℃.

[0011] Preferably, the ozone flow rate in the ozone atmosphere is 0.5-4 L / min. -1 .

[0012] Preferably, the calcination is carried out at 200-250°C for 72-108 hours.

[0013] Preferably, the number of roots is 5-100.

[0014] The SSZ-13 zeolite membrane prepared by the above method can be used in CO2 / CH4 separation.

[0015] Compared with the prior art, the present invention has the following beneficial effects: For the large-scale production of SSZ-13 zeolite membranes, this invention synergistically improves membrane performance and product yield at two core levels: synthesis kinetics and microstructure control. First, by introducing Na2S2O8 as a key additive into the synthesis solution, the generated hydroxyl radicals significantly lower the nucleation barrier, shortening the traditional crystallization process (which typically takes several days) to approximately 24 hours. While ensuring rapid membrane growth, the "self-repair" effect of free radicals effectively suppresses defect generation, thereby improving production efficiency while ensuring high quality and a high yield for each batch of membrane products. Second, by precisely controlling the matching index between seed crystal size and carrier pore size within the optimized range of 0.5-1.0, the foundation for seed layer laying and subsequent crystal growth is fundamentally optimized, effectively avoiding membrane structure inhomogeneity caused by seed infiltration or overgrowth. The combination of these two key technologies enables the large-scale fabrication of membranes (such as membrane modules up to 40 cm long) to exhibit excellent reproducibility in terms of thickness, density, and separation performance, with CO2 / CH4 separation selectivity consistently above 120, achieving efficient and stable manufacturing of high-throughput, high-selectivity membrane products. Attached Figure Description

[0016] Figure 1 Scanning electron microscopy (SEM) characterization results of SSZ-13 zeolite seeds and their corresponding films in Example 1: (ac) Surface morphology of seed layers with average particle sizes of (a) 100 nm, (b) 200 nm and (c) 450 nm; (df) Top view of SSZ-13 zeolite films synthesized using the corresponding seeds and (gi) SEM image of cross-section; Figure 2 Top view (left) and cross-sectional scanning electron microscope (SEM) image (right) of SSZ-13 zeolite membranes obtained at different synthesis times (t) in Example 2: (a, b) 10 hours, (c, d) 24 hours, (e, f) 48 hours; Figure 3 Effects of (a) synthesis time (t) and (b) sodium persulfate (Na2S2O8) molar ratio (r) on the CO2 / CH4 separation performance of SSZ-13 zeolite membrane in Examples 2 and 3; Crystallization curves of SSZ-13 zeolite synthesized with different sodium persulfate molar ratios: (c) 0.01 and (d) 0.04; t0: induction period; t1: crystallization period.

[0017] Figure 4Example 4: Scalable preparation of SSZ-13 zeolite membrane, (a) photograph of batch synthesis scaffold; (b) top view of 40 cm long SSZ-13 zeolite membrane and (c) cross-sectional scanning electron microscope (SEM) image; (d) CO2 / CH4 separation performance of single batch synthesis membrane; (e) effect of CO2 molar fraction on gas permeation flux and selectivity (M46); Figure 5 Example 5: (a) Schematic diagram of an infinitely long SSZ-13 zeolite membrane model operating under a single-stage process without purge gas; (b) Schematic diagram along the membrane area (S mem (c) Gas concentration distribution curves (unit: square meters); (d) Carbon dioxide removal rate and methane loss rate as a function of feed flow rate (Nm³). 3 ·m -2 ·h -1 (d) Schematic diagram of the two-stage membrane system process for biogas purification. Detailed Implementation

[0018] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0019] Example 1: This embodiment uses the following steps to prepare the SSZ-13 zeolite membrane: (1) SSZ-13 seeds were prepared by zeolite interconversion method. The molar composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: 0.01 Na2S2O8: 0.4 TMAdaOH: 5.0 H2O. 0.1wt.% SSZ-13 seeds were added and hydrothermally reacted at 160℃ for 24-120h. After centrifugation, washing, drying and calcination at 550℃, seed crystals were obtained. Seed crystals with average particle sizes of 100, 200 and 450nm were obtained by controlling the synthesis time.

[0020] (2) Seed Coating and Membrane Synthesis: SSZ-13 seeds were coated onto the surface of an α-Al2O3 hollow fiber carrier with an average pore size of 250 nm using a dip-coating method. The composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: 0.01 Na2S2O8: 0.2 TMAdaOH: 0.12 Na2O: 44 H2O. The coated carrier was placed in a reaction vessel and reacted at 160℃ for 24 h. After the reaction, the template agent was removed by washing, drying, and ozone treatment to obtain the SSZ-13 zeolite membrane.

[0021] Example 2: This embodiment uses the following steps to prepare the SSZ-13 zeolite membrane: (1) SSZ-13 seeds were prepared by zeolite interconversion method. The molar composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: 0.01 Na2S2O8: 0.4 TMAdaOH: 5.0 H2O. 0.1wt.% SSZ-13 seeds were added and hydrothermally reacted at 160℃ for 24-120h. After centrifugation, washing, drying and calcination at 550℃, crystals with an average particle size of 200nm were obtained.

[0022] (2) Seed Coating and Membrane Synthesis: SSZ-13 seeds were coated onto the surface of an α-Al2O3 hollow fiber carrier with an average pore size of 250 nm using a dip-coating method. The composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: 0.01 Na2S2O8: 0.2 TMAdaOH: 0.12 Na2O: 44 H2O. The coated carrier was placed in a reaction vessel and reacted at 160℃. After the reaction, the template agent was removed by washing, drying, and ozone treatment to obtain the SSZ-13 zeolite membrane. In this example, the reaction times were 10 h, 24 h, and 48 h, respectively.

[0023] Example 3 This embodiment uses the following steps to prepare the SSZ-13 zeolite membrane: (1) SSZ-13 seeds were prepared by zeolite interconversion method. The molar composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: 0.01 Na2S2O8: 0.4 TMAdaOH: 5.0 H2O. 0.1wt.% SSZ-13 seeds were added and hydrothermally reacted at 160℃ for 24-120h. After centrifugation, washing, drying and calcination at 550℃, crystals with an average particle size of 200nm were obtained.

[0024] (2) Seed Coating and Membrane Synthesis: SSZ-13 seeds were coated onto the surface of an α-Al2O3 hollow fiber carrier with an average pore size of 250 nm using a dip-coating method. The composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: r Na2S2O8: 0.2 TMAdaOH: 0.12 Na2O: 44 H2O. The coated carrier was placed in a reaction vessel and reacted at 160℃ for 24 h. After the reaction, the template agent was removed by washing, drying, and ozone treatment to obtain the SSZ-13 zeolite membrane. In this embodiment, r was selected from 0, 0.005, 0.01, 0.02, and 0.04, respectively.

[0025] Example 4 This embodiment is used to realize the large-scale production of SSZ-13 zeolite membranes, and includes the following steps: This embodiment uses the following steps to prepare the SSZ-13 zeolite membrane: (1) SSZ-13 seeds were prepared by zeolite interconversion method. The molar composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: 0.01 Na2S2O8: 0.4 TMAdaOH: 5.0 H2O. 0.1wt.% of SSZ-13 seeds were added and hydrothermally reacted at 160℃ for 24-120h. After centrifugation, washing, drying and calcination at 550℃, crystals with an average particle size of 200nm were obtained.

[0026] (2) Seed coating and film synthesis: SSZ-13 seeds were coated onto the surface of an α-Al2O3 hollow fiber carrier with an average pore size of 250 nm using a dip-coating method. Figure 4 As shown in Figure a, 18 crystallized supports were assembled parallel to each other onto a support frame. The composition of the synthesized gel was: 1.0 SiO2: 0.005 Al2O3: 0.02 Na2S2O8: 0.2 TMAdaOH: 0.12 Na2O: 44 H2O. The assembled supports were placed in a reactor and reacted at 160℃ for 24 h. After the reaction, the template agent was removed by washing, drying, and ozone treatment to obtain the SSZ-13 zeolite membrane.

[0027] Example 5 This embodiment develops a one-dimensional steady-state mathematical model to simulate the CO2 / CH4 separation process in a hollow fiber zeolite membrane module. The model assumes ideal plug flow behavior and neglects radial and pressure drops along the fiber length. The mass balance of each species i (i = CO2, CH4) along the axial coordinate z is systematically described by the following ordinary differential equations (ODEs): Among them, F i The molar flow rate (mol·s) of species i -1 ), where 'a' represents the effective membrane area per unit length (m²). 2 ·m -1 ), J i Local transmembrane flux (mol·m -2 ·s -1 Local flux J i Controlled by the adsorption-diffusion mechanism and driven by the partial pressure difference across the membrane: Among them, P i Let i be the osmotic flux (mol·m -2 ·s -1 ).

[0028] The simulation involves the composition of the permeate x i Composed of y with the retained products i Nonlinear coupling between them. The local permeate composition is determined by an algebraic relationship derived from the flux ratio: Characterization The membrane samples prepared in Examples 1-3 were characterized by SEM and CO2 / CH4 separation were tested at a temperature of 25°C and a total feed flow rate of 400 mL / min. -1 The feed pressure (pf) is regulated within the range of 0.1 to 2.0 MPa via a back pressure regulator, while the permeation side is maintained at atmospheric pressure. Argon is used as the purge gas at a rate of 20 mL / min. -1 The flow rate is introduced into the permeation side.

[0029] Test Results Figure 1 The effect of seed crystals of different sizes on the membrane microstructure and separation performance in Example 1 is demonstrated. Figure 1 As can be seen from AC, a continuous and uniform seed layer was deposited on the carrier surface using the dip-coating method. For example... Figure 1 As can be seen from the data, all films exhibit dense, interactive growth, forming a continuous polycrystalline layer with the typical cubic morphology of SSZ-13. Figure 1 gi revealed a significant dependence of membrane thickness on seed size. Membranes synthesized from 100 nm seeds ( Figure 1 g) showed the thinnest molecular sieve layer (1.8 μm), but an intermediate transition layer of 2 μm was present. Increasing the seed size to 200 nm yielded a membrane of moderate thickness (2.5 μm) with a clear molecular sieve-support interface. Figure 1 In contrast, 450 nm seeds resulted in the thickest molecular sieve layer (4.3 μm, h). Figure 1 i). These results indicate that smaller seeds provide higher nucleation density, enhancing competitive growth among crystals and resulting in thinner films; while larger seeds allow crystals to grow more unrestricted, leading to thicker selective layers.

[0030] Table 1 shows the separation performance of membrane samples prepared with different seed size to support pore size ratios (hereinafter referred to as "seed size ratio MI") for the CO2 / CH4 system. As shown in Table 1, the membrane with MI = 0.82 (200 nm seed) exhibits the best performance, with a CO2 permeation rate of (4.69 ± 0.38) × 10⁻⁶. -7 mol·m -2 ·s -1 ·Pa -1The CO2 / CH4 separation selectivity was 182 ± 18. For higher MI (1.80), excessive thickness increased mass transfer resistance (4.3 μm vs. 2.5 μm), thus reducing the permeation rate. For smaller MI (0.42), seed permeation generated additional transport resistance at the interface.

[0031] Table 1. Separation performance test results of membrane samples prepared with different seed size ratios. a) Test conditions: 400 mL·min -1 Equimolar feed, temperature 25℃, pressure 0.2MPa.

[0032] b) nm; c) ×10 -7 mol·m -2 ·s -1 ·Pa -1 ; d) ×10 -9 mol·m -2 ·s -1 ·Pa -1 .

[0033] Figure 2 SEM images of the film surface and cross-section at different crystallization times (10h, 24h, and 48h) in Example 2 are shown. As can be seen from the figures, the film synthesized at 10h exhibits incomplete intergranular growth, characterized by visible intergranular gaps and non-zeolite defects. Figure 2 a). Cross-sectional view ( Figure 2 (b) Confirmed a relatively thin and discontinuous molecular sieve layer (approximately 1.4 μm). Extending the hydrothermal synthesis time to 24 hours resulted in denser, intergrowth crystals, forming a continuous molecular sieve membrane layer. Figure 2 c), the thickness increases to approximately 2.3 μm ( Figure 2 d). Further extending the synthesis time to 48 hours resulted in negligible morphological changes. Figure 2 The thickness increased slightly (approximately 2.4 μm), indicating that the membrane growth had reached a self-limiting stage, consistent with the "self-repairing" behavior of the molecular sieve layer. The evolution of CO2 / CH4 separation performance correlated well with these microstructural changes. Figure 3 a) As the synthesis time increased from 10 hours to 24 hours, the CO2 permeation rate increased from 4.62 × 10⁻⁶. -7 mol·m -2 ·s -1 ·Pa -1 It monotonically decreased to 2.38 × 10 -7 mol·m -2 ·s-1 ·Pa -1 The CO2 / CH4 selectivity increased sharply from 43 to 124. This phenomenon indicates that the membrane gradually densifies and non-selective defects are eliminated. After more than 24 hours (up to 48 hours), the separation performance tends to stabilize (selectivity approximately 124-144), indicating that the membrane structure has reached dynamic equilibrium. The CO2 permeation rate of the SSZ-13 molecular sieve membrane prepared at r=0 is 4.8 × 10⁻⁶. -7 mol·m -2 ·s -1 ·Pa -1 However, the CO2 / CH4 selectivity was relatively low, at 77. In contrast, the current Na2S2O8-assisted synthesis achieved significantly higher selectivity in the same time frame (123). The effect of the Na2S2O8 / SiO2 molar ratio (r) was investigated at 160°C ( Figure 3 (b) In the absence of Na₂S₂O₈ (r = 0), the CO₂ permeation rate of the membrane is 2.25 × 10⁻⁶. -7 mol·m -2 ·s -1 ·Pa -1 The CO2 / CH4 selectivity was moderate, at 80. The introduction of trace amounts of Na2S2O8 (r = 0.005–0.01) improved both the CO2 permeation rate and the CO2 / CH4 separation selectivity. However, higher concentrations (r > 0.02) led to a sharp deterioration in separation performance, with selectivity decreasing to 20–67. Figure 3 b). The harmful effects of excess Na2S2O8 are elucidated by the crystallization kinetics of SSZ-13 molecular sieve crystals. Figure 3 cd).

[0034] Figure 4 This demonstrates the batch synthesis of a 40 cm long SSZ-13 molecular sieve membrane using a stackable, rapidly assembled process. SEM reveals a uniform polycrystalline layer with an average grain size of approximately 3 μm, comparable to the membrane thickness. Figure 4 (b, c) Using an equimolar CO2 / CH4 mixture at 0.2 MPa and a feed flow rate of 2 L / min -1 The separation performance was evaluated (without purge gas). In one batch (n = 18, M33–M50), the membrane exhibited a separation efficiency of (2.2 ± 0.69) × 10⁻⁶. -7 mol·m -2 ·s -1 ·Pa -1 CO2 permeation rate and CO2 / CH4 selectivity of 118 ± 22 Figure 4d) demonstrates the good reproducibility of the scale-up scheme. Subsequently, the membrane M46 was further tested using CO2 / CH4 mixtures with different CO2 molar fractions at different feed pressures. Figure 4 e). For all tested pressures (0.8, 1.4, and 2.0 MPa), the separation performance tended to stabilize when the feed CO2 fraction exceeded 30% (volume percentage, the same below). This is consistent with the preferential adsorption of CO2 leading to near saturation of adsorption sites in the CHA cages, thus exhibiting a weak dependence on further increases in CO2 concentration. Due to competitive adsorption, the molecular sieve channels were mainly occupied by CO2, which effectively hindered CH4 transport through molecular sieving and channel blockage effects. Further increases in feed CO2 concentration had a negligible effect on the adsorbed phase composition, resulting in stable performance. The linear correlation between CO2 flux and concentration indicates that CO2 transport is controlled by partial pressure driving forces.

[0035] To clarify the axial concentration distribution within the membrane module ( Figure 5 a) A numerical simulation framework incorporating concentration-dependent permeation rates was developed. The simulated CO2 concentrations in the permeate and retrieval streams showed excellent agreement with experimental data, validating the reliability of the numerical model in predicting the separation of binary mixtures under the studied conditions. Based on the reproduced model, the separation of binary mixtures under typical operating conditions (feed flow rate 2 L / min) was systematically investigated. -1 Separation behavior and membrane area (S) under the conditions of feed pressure 2 MPa, permeate side pressure 0.1 MPa, CO2 concentration 50%, and no purge gas: mem The functional relationship between ). Figure 5 b illustrates the evolution of concentration distribution along the module as the membrane area increases. The CO2 concentration on the filtration side initially decreases rapidly, then decreases with increasing S... mem The increase and decrease are more gradual. This behavior is essentially related to the local CO2 partial pressure difference ( The distribution of CO2 is related to the initial high partial pressure of CO2 in the feed, which provides a significant driving force, resulting in a high CO2 removal rate. However, as CO2 is gradually removed, localized... The reduction in membrane area leads to a decrease in local permeation rate. Furthermore, this effect is observed over a wider range of membrane areas (up to 0.18 m²). 2 A clear trade-off between CO2 removal and CH4 loss was observed within the sample. From this global perspective, when S... mem ≤ 0.04m 2 At that time, due to the limited stage cutting, CH4 loss is negligible, while CO2 removal rate increases with S. mem Increase. If it exceeds this range, further increase S. mem The gain on CO2 recovery decreases, but leads to a more significant increase in CH4 loss. This trend highlights the diminishing returns region, where the marginal gain in CO2 removal is offset by the excessive loss of valuable CH4 products. For ease of process design, Figure 5 c summarizes the relationship between CO2 removal rate, CH4 loss rate, and treatment capacity. The optimal range highlighted in cyan represents the operating window that meets the predetermined constraints on CH4 loss and CO2 removal rate, providing practical guidance for selecting membrane area and treatment capacity. Figure 5 As shown in d, a two-stage 220m 2 The SSZ-13 zeolite membranes are connected in series. The permeate side of the first-stage membrane (operating pressure 2.0 MPa, room temperature) is connected to the feed side of the second-stage membrane (operating pressure 2.1 MPa) via a compressor. The permeate side of the second-stage membrane is connected to the feed side of the first-stage membrane. The feed gas is 40% CO2 and 60% CH4. A product gas with a concentration of 98% CH4 and 2% CO2 can be obtained on the permeate side of the first-stage membrane, and a gas with a concentration of 99% CO2 and 1% CH4 can be obtained on the permeate side of the second-stage membrane. The CH4 loss rate is only 1.78%.

[0036] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for rapidly preparing SSZ-13 zeolite membranes using a Na2S2O8-assisted strategy, characterized in that, Includes the following steps: (1) Prepare SSZ-13 molecular sieve as seed crystal; (2) Select a carrier with a seed particle size to carrier pore size ratio of 0.5-1, and coat the seed on the carrier surface to form a seeded carrier; (3) Assemble several seed carriers in parallel on a support frame and immerse them as a whole in a casting solution with a molar ratio of 1.0 SiO2:0.001-0.01 Al2O3:0.005-0.04 Na2S2O8:0.1-0.5 TMAdaOH:0.1-0.2 Na2O:20-100 H2O. Then immerse the seed carriers in the casting solution for hydrothermal crystallization for 10-36 hours to form a preform film. (4) The embryo membrane is calcined in an ozone atmosphere to remove the template agent, thereby obtaining SSZ-13 zeolite membrane.

2. The method according to claim 1, characterized in that, The SSZ-13 molecular sieve is formed through a molecular sieve conversion pathway.

3. The method according to claim 1, characterized in that, The particle size of SSZ-13 molecular sieve is 100-450nm.

4. The method according to claim 1, characterized in that, The seed crystals are prepared into a seed crystal suspension of 0.1-2 wt%, and the seed crystals are coated onto the carrier surface by one or more of the following methods: immersion coating, vacuum coating, and wiping coating.

5. The method according to claim 1, characterized in that, The carrier is one of sheet type, tubular type, single-channel hollow fiber or multi-channel hollow fiber.

6. The method according to claim 1, characterized in that, The hydrothermal synthesis temperature is 150-180℃.

7. The method according to claim 1, characterized in that, The ozone flow rate in the ozone atmosphere is 0.5-4 L / min. -1 .

8. The method according to claim 1, characterized in that, The roasting is carried out at 200-250℃ for 72-108 hours.

9. The method according to claim 1, characterized in that, The number of roots is 5-100.

10. The application of the SSZ-13 zeolite membrane prepared according to claim 1 in CO2 / CH4 separation.

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