Method for rapidly preparing SSZ-13 molecular sieve membrane based on double-template system

Abstract

The invention provides a method for rapidly preparing an SSZ-13 molecular sieve membrane based on a double-template system, and belongs to the field of preparation and application of molecular sieve membrane materials. The polymer ammonium is introduced into the sol and seed crystal suspension, so that the nucleation and crystallization process in the synthesis system is obviously accelerated, the traditional synthesis time can be shortened by 50% or above, and the rapid growth of the SSZ-13 seed crystal on the surface of the porous carrier is realized. Based on the synergistic effect of the double template agents, the preparation repeatability of the SSZ-13 molecular sieve membrane is effectively improved, and large-scale application of high-quality membrane products is facilitated. The SSZ-13 molecular sieve membrane shows excellent separation performance in CO2 / CH4 mixed gas, and has remarkable industrial application value in the field of natural gas decarburization.

Description

Technical Field

[0001] The present invention provides a method for rapidly preparing an SSZ-13 molecular sieve membrane based on a dual-template agent system, belonging to the field of preparation of molecular sieve membrane materials. Background Art

[0002] With the low-carbon transformation of the global energy structure, the high-concentration CO2 associated with natural gas production not only reduces the calorific value of natural gas but also exacerbates pipeline corrosion. Traditional decarbonization processes such as low-temperature distillation and adsorption have defects of high energy consumption and equipment corrosion. Developing new efficient and energy-saving technologies has become an urgent need in the industry. Membrane separation technology has shown significant industrial application prospects due to its low energy consumption, high selectivity, simple operation, and cost advantages. Molecular sieve membranes have unique thermal stability and chemical stability and have become a research hotspot in the field of membrane separation due to their excellent separation selectivity. SSZ-13 molecular sieve is a microporous crystalline material with a chabazite (CHA) topological structure, having a regular three-dimensional pore system with a pore size of 0.38 nm. The characteristic pore size of the SSZ-13 molecular sieve membrane is close to the kinetic diameter of CO2 molecules (0.33 nm), making it exhibit excellent selective adsorption and pore size screening characteristics and showing significant application advantages in the CO2 / CH4 gas separation system.

[0003] Currently, the preparation technology of SSZ-13 molecular sieve membranes faces many challenges: (1) The induction period of the synthesis system is too long, resulting in a slow nucleation and crystallization rate. The conventional preparation process needs to last for more than 2 days, leading to excessive energy consumption during the synthesis process; (2) The membrane layer prepared with too long synthesis time becomes thick, causing an increase in mass transfer resistance and reducing the permeation rate of the membrane. To address the above problems, in previous work (patent for invention CN104289115A), the research group used a combination of two or three templating agents among adamantyltrimethylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide to prepare SSZ-13 molecular sieve membranes, which can shorten the membrane crystallization time to 36 h. Although it is described in the patent document that "hydrothermal crystallization is carried out for 8 to 96 h", it is difficult to prepare membrane materials with good performance within a crystallization time of less than 36 h. Moreover, the separation performance of the SSZ-13 molecular sieve membranes prepared by the above method still needs to be further improved. Therefore, it is urgent to optimize the existing preparation method of SSZ-13 molecular sieve membranes to obtain membrane materials with a short preparation time and better separation performance. Summary of the Invention

[0004] The present invention introduces polymer ammonium into the SSZ-13 molecular sieve membrane synthesis sol and seed suspension, forms a dual-template synergistic effect with a small molecule structure-directing template agent, promotes the nucleation and crystallization process in the synthesis system, and realizes the rapid preparation of high-quality SSZ-13 molecular sieve membranes.

[0005] Specifically, the present invention provides a method for rapidly preparing an SSZ-13 molecular sieve membrane based on a dual-template agent system. A dual-template agent is used in the synthesis process of the SSZ-13 molecular sieve membrane. The dual-template agent includes a structure-directing template agent and an auxiliary template agent; the auxiliary template agent is a polymeric ammonium.

[0006] Preferably, the structure-directing template agent is any one or more of N-N-N-trimethyladamantyl ammonium hydroxide, N-N-N-trimethyladamantyl ammonium bromide, N-N-N-trimethyladamantyl ammonium iodide, or tetraethyl ammonium hydroxide, and the polymeric ammonium is any one or more of mebezonium bromide, poly(methacryloyloxyethyl trimethyl ammonium chloride), poly(vinylbenzyl trimethyl ammonium chloride), or poly(diallyl dimethyl ammonium chloride).

[0007] According to the method described in claim 1, characterized in that the structure-directing template agent is added to the SSZ-13 molecular sieve membrane synthesis sol, and the polymeric ammonium is added to the SSZ-13 molecular sieve membrane synthesis sol or the seed suspension.

[0008] Preferably, the addition amount of the polymeric ammonium in the SSZ-13 molecular sieve membrane synthesis sol or the seed suspension is 0.02 - 2.0 wt%.

[0009] Preferably, the method includes the following steps:

[0010] (1) Synthesize SSZ-13 molecular sieve seeds;

[0011] (2) Coat the SSZ-13 molecular sieve seeds on the surface of the carrier;

[0012] (3) Prepare the synthesis solution of the SSZ-13 molecular sieve membrane;

[0013] (4) Transfer the carrier obtained in step (2) and the membrane synthesis solution obtained in step (3) to a reaction kettle, and hydrothermally crystallize to obtain the SSZ-13 molecular sieve membrane.

[0014] Preferably, the synthesis step of the SSZ-13 molecular sieve seeds in step (1) includes: mixing a structure-directing template agent (SDA), sodium hydroxide, a silicon source, an aluminum source, and deionized water to form a sol, stirring and aging at room temperature for 12 - 96 h. The molar ratio of the sol is: SiO2 / Al2O3 = 10 - 300, SDA / SiO2 = 0.1 - 2.0, NaOH / SiO2 = 0.1 - 1.5, H2O / SiO2 = 5 - 120; the sol is placed in a reaction kettle and hydrothermally synthesized at 110 - 260 °C for 1 - 7 d. The product is cooled, washed, centrifuged, and dried to obtain the SSZ-13 molecular sieve seeds.

[0015] Preferably, in the step (2), the support has a symmetric or asymmetric structure, and its shape includes one of plate-like, hollow fiber-like, tubular and multi-channeled shapes, with an average pore size of 50 - 1000 nm and a porosity of 30% - 60%; the SSZ-13 molecular sieve seeds are coated on the surface of the support by one or a combination of methods such as wiping, dipping, spin-coating, spraying or vacuum pumping; when the dipping method is used, the concentration of the SSZ-13 molecular sieve seed suspension is preferably 0.0125 - 2 wt%, and the crystal coating time is 20 - 90 s.

[0016] Preferably, in the step (3), the preparation method of the SSZ-13 molecular sieve membrane synthesis sol is: mixing a structure-directing template agent (SDA), sodium hydroxide, a silicon source, an aluminum source and deionized water, and stirring and aging at room temperature for 2 - 72 h. The sol molar ratio of the SSZ-13 molecular sieve membrane synthesis sol is: SiO2 / Al2O3 = 10 - 300, SDA / SiO2 = 0.1 - 1.0, NaOH / SiO2 = 0.1 - 1.5, H2O / SiO2 = 10 - 200.

[0017] Preferably, the aluminum source used in the steps (1) and (3) is any one or several of aluminum hydroxide, sodium aluminate, boehmite, aluminum isopropoxide, aluminum butoxide, aluminum foil, aluminum powder or alumina; the silicon source is any one or several of silica sol, silicon powder, silicate ester or sodium silicate.

[0018] Preferably, in the step (4), the crystallization temperature is 120 - 240 °C and the crystallization time is 2 - 48 h; after the reaction is complete, an SSZ-13 molecular sieve membrane is obtained after washing, drying and calcination.

[0019] Preferably, the structure-directing agent SDA is selected from one or several of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide, N,N-diethyl-2,6-dimethylpiperidinium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide or tetraethylammonium hydroxide.

[0020] Compared with the prior art, the present invention provides a method for rapidly preparing an SSZ-13 molecular sieve membrane based on a dual-template agent system. By using a small molecule structure-directing agent and a polymeric ammonium as a synergistic organic template agent, the film-forming uniformity is improved and the membrane synthesis time is shortened, realizing precise control of the film layer thickness, so as to synthesize a high-performance SSZ-13 molecular sieve membrane on a porous support. This membrane exhibits excellent separation performance in the CO2 separation of a CO2 / CH4 mixture and has good application prospects for natural gas decarbonization. Description of the Drawings

[0021] Figure 1 SEM and XRD diagrams of the SSZ-13 molecular sieve seeds in Example 1;

[0022] Figure 2 SEM images (a - surface, b - cross - section) and XRD pattern of SSZ - 13 zeolite membrane M1 prepared by adding emepronium bromide to the sol in Example 1;

[0023] Figure 3 SEM images (a - surface, b - cross - section) and XRD pattern of SSZ - 13 zeolite membrane M8 prepared by adding emepronium bromide to the seed suspension in Example 8;

[0024] Figure 4 Single - gas permeation rate diagrams of SSZ - 13 zeolite membranes prepared by adding emepronium bromide to the sol and the seed suspension in Example 1 membrane M1 and Example 8 membrane M8 respectively. Detailed implementation manners

[0025] Example 1

[0026] (1) Preparation of SSZ - 13 zeolite seeds: Mix N - N - N - trimethyladamantylammonium hydroxide, sodium hydroxide, silicon source, aluminum source and deionized water to form a synthesis sol, stir and age at room temperature for 24 h. The molar ratio of the sol is: SiO2 / Al2O3 = 40, SDA / SiO2 = 0.4, NaOH / SiO2 = 0.2, H2O / SiO2 = 50. Place the synthesis sol in a reaction kettle, hydrothermally synthesize at 160 °C for 4 d. The obtained product is cooled, washed, centrifuged and dried, and calcined at 500 °C to obtain SSZ - 13 zeolite seeds.

[0027] (2) Coating SSZ - 13 zeolite seeds on a porous support: Select an asymmetric porous alumina tube with a pore diameter of 200 nm as the support. After the support is cleaned and dried, coat the outer surface of the support with SSZ - 13 zeolite seeds by the dip - coating method. Specifically, disperse the seeds prepared in step (1) in ethanol to form a seed suspension with a mass fraction of 0.1 wt%, and place the support in this suspension for 60 s.

[0028] (3) Mix N - N - N - trimethyladamantylammonium hydroxide, sodium hydroxide and deionized water, stir for 30 min; then add 0.5 wt% of emepronium bromide, stir for 20 min; then add the aluminum source, stir for 1 h; finally add the silicon source, and stir and age at room temperature for 24 h. The molar ratio of the sol is: SiO2 / Al2O3 = 100, SDA / SiO2 = 0.5, NaOH / SiO2 = 0.5, H2O / SiO2 = 50.

[0029] (4) Transfer the carrier coated with SSZ-13 molecular sieve seeds obtained in step (2) and the membrane synthesis sol obtained in step (3) into a reaction kettle, and then hydrothermally crystallize at 160 °C for 1 day. After the reaction is complete, after washing and drying, calcine at 450 °C for 24 h to remove the template agent (the heating and cooling rates are both 1 °C / min) to obtain the SSZ-13 molecular sieve membrane, and the prepared membrane is marked as M1.

[0030] Figure 1 a in is the SEM image of the SSZ-13 molecular sieve seeds, Figure 1 b in is the XRD pattern of the SSZ-13 molecular sieve seeds. The particle size of the SSZ-13 molecular sieve seeds is about 200 - 300 nm, with good monodispersity and uniform particle size distribution. XRD shows high crystallinity, and no obvious impurity crystal phases are observed.

[0031] The gas separation performance of the molecular sieve membrane is tested with an equimolar CO2 / CH4 mixed gas, and is represented by two parameters: the gas permeation rate P and the separation selectivity α. Among them, the gas permeation rate P represents the total amount of gas passing through a unit membrane area per unit time and unit pressure, P = N / (A × t × ΔP), and the unit is mol / (m 2 s Pa); the separation selectivity α is used to evaluate the level of membrane separation efficiency, α = P A / P B . In the formula, P A and P B represent the permeation rates of the gas on the permeate side and the feed side, respectively.

[0032] The membrane M1 is used for the separation of equimolar mixed gases, and the separation performance results are shown in Table 1.

[0033] Example 2

[0034] The membrane preparation method is similar to that in Example 1. The difference is that 0.1 wt% of emepronium bromide is added to the sol in step (3), and the other steps are the same as those in Example 1. The prepared membrane is marked as M2, and this membrane is used for the gas separation performance test of the CO2 / CH4 system, and its separation performance is shown in Table 1.

[0035] Example 3

[0036] The membrane preparation method is similar to that in Example 1. The difference is that 0.2 wt% of emepronium bromide is added to the sol in step (3), and the other steps are the same as those in Example 1. The prepared membrane is marked as M3, and this membrane is used for the gas separation performance test of the CO2 / CH4 system, and its separation performance is shown in Table 1.

[0037] Example 4

[0038] The membrane preparation method is similar to that of Example 1, except that 1.0 wt% of emepronium bromide is added to the sol in step (3), and the remaining steps are the same as those in Example 1. The prepared membrane is labeled as M4, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. The separation performance is shown in Table 1.

[0039] Example 5

[0040] The membrane preparation method is similar to that of Example 1, except that 2.0 wt% of emepronium bromide is added to the sol in step (3), and the remaining steps are the same as those in Example 1. The prepared membrane is labeled as M5, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. The separation performance is shown in Table 1.

[0041] Example 6

[0042] The membrane preparation method is similar to that of Example 1. The difference lies in that the hydrothermal reaction time is 12 h in step (4), and the remaining steps are the same as those in Example 1. The prepared membrane is labeled as M6, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. The separation performance is shown in Table 1.

[0043] Example 7

[0044] The membrane preparation method is similar to that of Example 1. The difference lies in that the hydrothermal reaction time is 48 h in step (4), and the remaining steps are the same as those in Example 1. The prepared membrane is labeled as M7, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. The separation performance is shown in Table 1.

[0045] Example 8

[0046] The difference from Example 1 is that in step (3), emepronium bromide is not added to the synthetic gel, but 0.5 wt% of emepronium bromide is added to the prepared seed suspension in step (2) and ultrasonicated for 1 h, and the remaining steps are the same as those in Example 1. The prepared membrane is labeled as M8.

[0047] Figure 3 The surface and cross-section SEM images and XRD patterns of the SSZ-13 zeolite membrane M8 prepared by adding a specific concentration of emepronium bromide to the seed suspension are shown. As can be seen from the figure, the membrane surface shows a typical cubic crystal morphology of SSZ-13, without visible defects and impurity crystal phases on the membrane surface, and the membrane layer thickness is 1.7 μm.

[0048] Figure 4 The single gas permeation performance test results of the membrane M8 for H2, CO2, N2, CH4, C3H8, and SF6 are shown. The test conditions are 25 °C and 0.2 MPa. It can be seen that the SSZ-13 zeolite membrane has a preferential permeability to CO2, and the ideal separation selectivity of the membrane for CO2 / CH4 is 180.

[0049] The test results of the separation performance of the SSZ-13 molecular sieve membrane M8 for the CO2 / CH4 (50 / 50) mixed gas are shown in Table 1. At 25 °C, 0.2 MPa, and a feed flow rate of 4 L / min, the CO2 permeation rate of the membrane is 16.0×10 -7 mol / (m 2 s Pa), and the CO2 / CH4 selectivity is 180.

[0050] Example 9

[0051] The membrane preparation method is similar to that of Example 8, except that 0.1 wt% of hexadecyltrimethylammonium bromide is added to the seed suspension in step (2), and the remaining steps are the same as those of Example 8. The prepared membrane is labeled M9, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. Its separation performance is shown in Table 1.

[0052] Example 10

[0053] The membrane preparation method is similar to that of Example 8, except that 1.0 wt% of hexadecyltrimethylammonium bromide is added to the seed suspension in step (2), and the remaining steps are the same as those of Example 8. The prepared membrane is labeled M10, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. Its separation performance is shown in Table 1.

[0054] Example 11

[0055] The membrane preparation method is similar to that of Example 8, except that the hydrothermal reaction time is 12 h in step (4), and the remaining steps are the same as those of Example 8. The prepared membrane is labeled M11, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. Its separation performance is shown in Table 1.

[0056] Example 12

[0057] The membrane preparation method is similar to that of Example 8, except that the hydrothermal reaction time is 48 h in step (4), and the remaining steps are the same as those of Example 8. The prepared membrane is labeled M12, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. Its separation performance is shown in Table 1.

[0058] Comparative Example 1

[0059] The synthesis method and raw materials used are similar to those of Example 1, except that hexadecyltrimethylammonium bromide is not added and a single template agent is used, and the remaining steps are the same as those of Example 1. The prepared membrane is labeled M13, and this membrane is used for the gas separation performance test of the CO2 / CH4 system. Its separation performance is shown in Table 1.

[0060] Comparative Example 2

[0061] The synthesis method and raw materials used were similar to those in Comparative Example 1, except that the synthesis time was 48 h, and the remaining steps were the same as those in Example 1. The prepared membrane was labeled as M14, and the gas separation performance of this membrane for the CO2 / CH4 system was tested, and the separation performance is shown in Table 1.

[0062] Table 1 Separation performance of CO2 / CH4 mixed gas of SSZ-13 molecular sieve membrane

[0063]

[0064] In this patent, the preparation efficiency and separation performance of SSZ-13 molecular sieve membrane were significantly optimized by introducing a dual-template system (structure-directing template + polymeric ammonium). First, the effects of the dual-template on shortening the synthesis time and improving the separation performance were investigated: In Comparative Example 1 (M13, without adding emepronium bromide), the CO2 / CH4 selectivity was only 2 within 24 hours of synthesis time, while in Example 1 (M1, adding 0.5% emepronium bromide to the sol), the selectivity was as high as 190 within the same time, and the CO2 permeation rate increased by 20% (2400 vs. 2000×10 -9 mol / (m 2 ·s·Pa)); this indicates that the introduction of polymeric ammonium significantly accelerated the nucleation and crystallization process, enabling the formation of a dense structure in the membrane layer in a shorter time, thus achieving both high selectivity and permeation rate. In addition, the CO2 / CH4 selectivity of Example 7 (M7, 48 hours) was further increased to 330, but the CO2 permeation rate decreased to 1400×10 -9 mol / (m 2 ·s·Pa), indicating that appropriately extending the crystallization time can optimize the density of the membrane layer, and the dual-template system can still achieve high performance on the basis of shortening the synthesis time. Then, the effects of different addition amounts and different addition methods of the auxiliary template were investigated: When adding emepronium bromide to the sol (Examples 1-5), when the addition amount was 0.5% (M1), both the CO2 / CH4 selectivity (190) and the CO2 permeation rate (2400×10 -9 mol / (m 2 ·s·Pa)) reached the peak values; excessive addition (such as M5, 2.0%) led to a sudden drop in the CO2 / CH4 selectivity to 90, and the CO2 permeation rate decreased to 560×10 -9 mol / (m 2 ·s·Pa), indicating that there is an optimal addition amount range (0.02-2.0 wt%). If the polymeric ammonium was added to the seed suspension (Example 8, M8), the CO2 / CH4 selectivity remained 180, but the CO2 permeation rate (1600×10 -9 mol / (m 2·s·Pa)) is lower than that of the sol addition method, indicating that different addition methods of polymeric ammonium will affect the film growth mechanism, and adding in the sol is more conducive to quickly constructing a continuous and dense film structure. From the balance of synthesis time and membrane performance, although Example 6 (M6, 12 hours) shortens the synthesis time to 12 hours, the selectivity is only 2, and the CO2 permeation rate is as high as 2700×10 -9 mol / (m 2 ·s·Pa), indicating that there are defects in the film layer and gas permeates through non-selective pores; while in Example 11 (M11, addition of seed suspension + 12 hours), the selectivity is even as low as 1, further verifying that too short a time will lead to incomplete symbiotic growth of the film layer, with cracks, pinholes and other defects. In contrast, Example 1 (24 hours) achieved a high selectivity (190) within the optimal synthesis time, proving that the dual-template system effectively balanced the synthesis time and separation performance by accelerating nucleation. In Comparative Examples 1-2 (without using polymeric ammonium), the CO2 / CH4 selectivities of M13 (24 hours) and M14 (48 hours) are 2 and 60 respectively, significantly lower than all examples. Especially, the CO2 / CH4 selectivity (60) of M14 at 48 hours is still much lower than that of Example 7 (330), indicating that it is difficult for a single-template system to make up for the lack of separation performance by extending the synthesis time, further highlighting the key role of the synergistic effect of the dual-template.

[0065] In summary, through the synergistic effect of the dual-template, the synthesis time of the SSZ-13 molecular sieve membrane in the present invention is shortened from more than 48 hours in the traditional method to 24 hours, while the CO2 / CH4 selectivity is increased to 180 - 330 (only 2 - 60 in the comparative examples), and the permeation rate is increased by nearly an order of magnitude. This breakthrough is attributed to the rapid auxiliary effect of polymeric ammonium on the synthesis system. By regulating the nucleation rate and the film growth direction, it optimizes the film structure while shortening the crystallization time, providing an efficient and scalable membrane separation solution for the field of natural gas decarbonization.

Claims

1. A method for rapidly preparing an SSZ-13 molecular sieve membrane based on a dual-template agent system, characterized in that, During the synthesis of SSZ-13 zeolite membrane, a dual template agent is used, and the dual template agent includes a structure-directing template agent and an auxiliary template agent; the auxiliary template agent is polymeric ammonium.

2. The method according to claim 1, wherein The structure-directing template agent is any one or several of N-N-N-trimethyladamantyl ammonium hydroxide, N-N-N-trimethyladamantyl ammonium bromide, N-N-N-trimethyladamantyl ammonium iodide, or tetraethylammonium hydroxide, and the polymeric ammonium is any one or several of mebezonium bromide, poly(methacryloyloxyethyl trimethylammonium chloride), poly(vinylbenzyltrimethylammonium chloride), or poly(diallyldimethylammonium chloride).

3. The method according to claim 1, wherein The structure-directing template agent is added to the SSZ-13 zeolite membrane synthesis sol, and the polymeric ammonium is added to the SSZ-13 zeolite membrane synthesis sol or the seed suspension.

4. The method according to claim 3, characterized in that The addition amount of the polymeric ammonium in the SSZ-13 zeolite membrane synthesis sol or the seed suspension is 0.02-2.0 wt%.

5. The method according to claim 1, characterized in that, The method includes the following steps: (1) Synthesize SSZ-13 zeolite seeds; (2) Coat the SSZ-13 zeolite seeds on the surface of the support; (3) Prepare the synthesis solution of the SSZ-13 zeolite membrane; (4) Transfer the support obtained in step (2) and the membrane synthesis solution obtained in step (3) to a reaction kettle, and hydrothermally crystallize to obtain the SSZ-13 zeolite membrane.

6. The method according to claim 5, wherein The synthesis steps of the SSZ-13 zeolite seeds in step (1) include: mixing a structure-directing template agent (SDA), sodium hydroxide, a silicon source, an aluminum source, and deionized water to form a sol, stirring and aging at room temperature for 12-96 h, and the molar ratio of the sol is: SiO2 / Al2O3 = 10-300, SDA / SiO2 = 0.1-2.0, NaOH / SiO2 = 0.1-1.5, H2O / SiO2 = 5-120; the sol is placed in a reaction kettle and hydrothermally synthesized at 110-260 °C for 1-7 d, and the product is cooled, washed, centrifuged, and dried to obtain the SSZ-13 zeolite seeds.

7. The method according to claim 5, wherein In step (2), the support has a symmetric or asymmetric structure, and its shape includes one of flat, hollow fiber, tubular, and multi-channel shapes, the average pore size is 50-1000 nm, and the porosity is 30%-60%; the SSZ-13 zeolite seeds are coated on the surface of the support by one or a combination of methods such as rubbing coating, dip coating, spin coating, spraying, or vacuum pumping coating; when using the dip coating method, the concentration of the SSZ-13 zeolite seed suspension is preferably 0.0125-2.0 wt%, and the coating time is 20-90 s.

8. The method according to claim 5, characterized in that In step (3), the preparation method of the SSZ-13 zeolite membrane synthesis sol is: mixing a structure-directing template agent (SDA), sodium hydroxide, a silicon source, an aluminum source, and deionized water, stirring and aging at room temperature for 2-72 h, and the molar ratio of the SSZ-13 zeolite membrane synthesis sol is: SiO2 / Al2O3 = 10-300, SDA / SiO2 = 0.1-1.0, NaOH / SiO2 = 0.1-1.5, H2O / SiO2 = 10-200.

9. The method according to claim 6 or 8, characterized in that, The aluminum source used in the steps (1) and (3) is any one or more of aluminum hydroxide, sodium aluminate, boehmite, aluminum isopropoxide, aluminum butoxide, aluminum foil, aluminum powder or alumina; the silicon source is any one or more of silica sol, silicon powder, silicate ester or sodium silicate.

10. The method according to claim 5, characterized in that, In the step (4), the crystallization temperature is 120 to 240 °C, and the crystallization time is 2 to 48 h; after the reaction is complete, the SSZ-13 molecular sieve membrane is obtained after washing, drying and calcination.

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