A supported MWW molecular sieve composite material, its preparation method and application

Abstract

This invention discloses a supported MWW molecular sieve composite material, its preparation method, and its applications. The supported MWW molecular sieve composite material comprises MWW molecular sieve and epoxy-modified polyethyleneimine supported on it. Based on the mass of the composite material, the epoxy compound content is 0.5%–28.0%, and the polyethyleneimine content is 5.0%–48.0%. Compared with existing technologies, the composite material of this invention can achieve a significant increase in carbon dioxide adsorption capacity under the same conditions, and can be used for the capture and separation of carbon dioxide from carbon dioxide-containing gases.

Description

Technical Field

[0001] This invention relates to a molecular sieve composite material, its preparation method and application, belonging to the field of carbon dioxide gas adsorption, separation and purification. Background Technology

[0002] The continuous rise in atmospheric carbon dioxide concentration has led to a series of problems, including climate change. Carbon dioxide capture, utilization, and storage (CCUS) has attracted increasing attention from researchers and industry as one of the solutions. Among these solutions, solid adsorption separation has broad development prospects as an important CCUS technology due to its advantages such as low regeneration energy consumption, easy equipment construction, and moderate output.

[0003] Previous studies have shown that preparing solid adsorbents by loading polyethyleneimine onto the porous support SBA-15 only increases the carbon dioxide adsorption capacity to 1.5 mmol / g at 40 °C, and only reaches 2.9 mmol / g at 55 °C (Catalysis Today, 2012, 194, 44-52). Other researchers have also loaded ethylenediamine onto H-type Y molecular sieves; although the resulting composites exhibit good stability, the carbon dioxide adsorption capacity at 40 °C does not exceed 1.9 mmol / g, indicating unsatisfactory practical results (Energy Environ. Sci., 2016, 9, 1803-1811). The sheet-like morphology and layered structure offer better development potential to some extent. CN104437418B discloses a layered material loaded with polyethyleneimine and its preparation method. Layered silicate materials loaded with polyethyleneimine can be prepared in a one-pot process under conditions of silicon source, heteroatom source, and alkaline substance. However, due to limitations in the synthesis conditions, the loading of polyethyleneimine is not high, resulting in limited improvement in carbon dioxide adsorption. Therefore, developing an adsorbent with strong selective carbon dioxide adsorption capacity is of significant importance. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a supported MWW molecular sieve composite material, its preparation method, and its applications. The composite material of this invention exhibits excellent performance in the selective adsorption of carbon dioxide.

[0005] The inventors discovered that using MWW molecular sieves as a carrier to load polyethyleneimine modified with epoxy compounds enhances the branching degree of the polymer chain segments. When loaded onto the layered structure of MWW molecular sieves, the chain segments are less prone to folding due to hydrogen bonds, thereby opening up the chain segments of the active amine groups, fully exposing the basic adsorption sites, and significantly improving the selective adsorption performance of carbon dioxide.

[0006] The first aspect of the present invention provides a supported MWW molecular sieve composite material, comprising MWW molecular sieve and epoxy-modified polyethyleneimine supported thereon, wherein, based on the mass of the composite material, the content of the epoxy compound is 0.5% to 28.0%, preferably 10.0% to 28.0%, and the content of the polyethyleneimine is 5.0% to 48.0%, preferably 25.0% to 45.0%.

[0007] Furthermore, based on the mass of the composite material, the content of the epoxy compound is 0.5% to 28.0%, preferably 10.0% to 28.0%, for example 2%, 5%, 10%, 13%, 14%, 18%, 20%, 22%, 26%, 28%, etc., and any value within the range formed by any two of these values.

[0008] Furthermore, based on the mass of the composite material, the content of polyethyleneimine is 5.0% to 48.0%, preferably 25.0% to 45.0%, for example 5%, 10%, 15%, 20%, 25%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, etc., and any value within the range formed by any two of these values.

[0009] Furthermore, the supported MWW molecular sieve composite material, based on the mass of the composite material, has an MWW molecular sieve mass content of 24.0% to 90.0%, preferably 25.0% to 55.0%, for example 24%, 29%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 55%, 60%, 70%, 80%, 90%, etc., and any value within any range formed by any two of these values.

[0010] Furthermore, the MWW molecular sieve includes at least one of SCM-1, SCM-2, SCM-6, MCM-22, and MCM-49, preferably SCM-1. Specifically, SCM-1 and SCM-2 are described in CN104511271B, and SCM-6 is described in CN105217651B.

[0011] Furthermore, the specific surface area of ​​the MWW molecular sieve is 30 to 1000 square meters per gram, preferably 300 to 700 square meters per gram.

[0012] Furthermore, the average molecular weight of the polyethyleneimine is 300 to 100,000, preferably 500 to 10,000.

[0013] Furthermore, the epoxy compound is one or both of propylene oxide and 1,2-epoxybutane.

[0014] The second aspect of the present invention provides a method for preparing the above-mentioned composite material, comprising: using MWW molecular sieve material as a carrier, loading epoxy-modified polyethyleneimine onto the carrier, and drying it to obtain the composite material.

[0015] Furthermore, the MWW molecular sieve includes at least one of SCM-1, SCM-2, SCM-6, MCM-22, and MCM-49. The MWW molecular sieve material exists in forms including, but not limited to, the raw powder obtained by direct synthesis, or the product after one-step calcination to remove the template agent.

[0016] Further, the method for loading epoxy-modified polyethyleneimine onto the carrier employs an impregnation method. The carrier is impregnated with an impregnation solution of epoxy-modified polyethyleneimine, and then dried to obtain the composite material. The preparation method of the epoxy-modified polyethyleneimine impregnation solution includes: dissolving polyethyleneimine in a solvent to prepare an impregnation solution, then adding an epoxy compound dropwise, and stirring for 10–480 minutes, preferably 30–300 minutes, to obtain the impregnation solution. The solvent is selected from one or more of methanol, ethanol, isopropanol, butanol, cyclohexanol, acetone, and water. In the impregnation solution, the mass concentration of the epoxy compound and polyethyleneimine is 0.05%–36%, preferably 1%–25%.

[0017] Furthermore, the impregnation temperature is 1–50°C, preferably 15–40°C, and more preferably 20–30°C.

[0018] Furthermore, the soaking time is 3 to 120 hours, preferably 6 to 72 hours.

[0019] Furthermore, after the impregnation reaction is completed, the drying method can be to obtain the corresponding product by vacuum heating drying, the temperature can be 40-150°C, more preferably 50-130°C, the drying time can be 2-50h, preferably 3-24h, and the solvent extracted by vacuum can be recycled and reused as the solvent of the impregnation liquid of the present invention.

[0020] A third aspect of the present invention provides the application of the above-described composite material in carbon dioxide adsorption.

[0021] Furthermore, the application includes: contacting a carbon dioxide-containing gas with the composite material to obtain a purified gas.

[0022] Furthermore, in the gas containing carbon dioxide, the volume content of carbon dioxide is 0.04% to 60%, and the other gases include at least one of nitrogen, methane, carbon monoxide, and hydrogen.

[0023] Further, the adsorption conditions are as follows: adsorption temperature of 10–85℃, preferably 40–75℃, pressure of 0.01–100 kPa, time of 1–60 min, and volume hourly space velocity of 5–2400 h⁻¹. -1 .

[0024] Furthermore, when the MWW molecular sieve composite material of the present invention is used for selective adsorption of carbon dioxide gas, it can be regenerated through multiple cycles. The regeneration conditions are as follows: under no heating or heating conditions, the heating temperature is 40-150°C, preferably 60-130°C, and at least one of nitrogen gas, carbon dioxide gas, and water vapor is used, or the tail gas after adsorption separation and purification is used to purge the composite material to achieve regeneration, or regeneration is achieved by depressurization degassing.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] The MWW molecular sieve composite material of this invention uses MWW molecular sieve as a carrier to load polyethyleneimine containing epoxy compounds, and has excellent selective adsorption performance of carbon dioxide. Attached Figure Description

[0027] Figure 1 The carbon dioxide gas adsorption-desorption isotherms at 40°C are shown for the molecular sieve composite material obtained in Example 1 and the porous silica composite material obtained in Comparative Example 1.

[0028] Figure 2 The carbon dioxide gas adsorption-desorption isotherms at 40°C are shown for the molecular sieve composite material obtained in Example 2 and the porous silica composite material obtained in Comparative Example 2.

[0029] Figure 3 The image shows a scanning electron microscope (SEM) image of the molecular sieve composite material obtained in Example 1.

[0030] Figure 4 The image shows a scanning electron microscope (SEM) image of the molecular sieve composite material obtained in Example 2.

[0031] Figure 5 Thermogravimetric analysis curve of the molecular sieve composite material obtained in Example 1 under carbon dioxide atmosphere;

[0032] Figure 6 The thermogravimetric analysis curve of the silica composite material obtained in Comparative Example 1 under carbon dioxide atmosphere is shown. Detailed Implementation

[0033] According to the present invention, the aforementioned molecular sieve composite material can be used in any physical form, such as powder, granules, or molded form (e.g., strips, cloverleaf shapes, etc.). These physical forms can be obtained in any manner conventionally known in the art, without particular limitation.

[0034] In the context of this specification, including in the following examples and comparative examples, the scanning electron microscope (SEM) used for molecular sieves and their composites is a model S-4800II field emission scanning electron microscope.

[0035] In the context of this specification, including in the following examples and comparative examples, the thermogravimetric analysis instrument used for molecular sieves and their composites is a TA Instrument SDT Q600 from the USA, and the tests are conducted using carbon dioxide (≥99.99%) and nitrogen (≥99.999%) atmospheres (switched between each other) at a rate of 100–200 mL / min.

[0036] In the context of this specification, including in the following examples and comparative examples, the specific surface area and isoporous structure characterization of the molecular sieves and their composites were determined by the nitrogen physical adsorption-desorption method (BET method): the nitrogen adsorption-desorption isotherm of the molecular sieves and their composites at 77 K was measured using an adsorption analyzer (Microtrac BELSORP max II adsorption analyzer), and then calculated using the BET equation and t-plot equation; the carbon dioxide adsorption capacity of the molecular sieves and their composites was characterized by the carbon dioxide gas adsorption-desorption isotherm: measured using the volumetric method, the carbon dioxide adsorption-desorption isotherm of the molecular sieves and their composites at 0–40 °C was measured using an adsorption analyzer. The experimental conditions for the molecular sieves and their composites were: measurement temperature -169 °C (i.e., 77 K, the boiling point of liquid nitrogen for testing nitrogen adsorption-desorption using the BET method) or 0–40 °C (which can be accurately adjusted using a circulating water bath), and the molecular sieve composites were pretreated in vacuum at 100–150 °C for 4–6 hours before measurement.

[0037] The present invention will be further described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0038] Example 1

[0039] 1.00 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 6 g of anhydrous methanol and stirred until homogeneous. Then, 0.587 g of 1,2-epoxybutane was added dropwise and stirred for 60 minutes to ensure complete reaction and form a homogeneous impregnation solution. Then, calcined SCM-1 molecular sieve powder (prepared according to Example I-1 of CN104511271B, with a specific surface area of ​​520 m²) was added. 21.00 g of methanol was stirred to ensure complete dispersion and continuously stirred in air at 25°C for 24 hours. After completion, the product was placed in a vacuum drying oven at 50°C and kept under vacuum for 5 hours to obtain the MWW molecular sieve composite material. The solvent methanol extracted under vacuum can be recovered and reused as the solvent for the impregnation solution of this invention.

[0040] Example 2

[0041] 1.50 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 8 g of anhydrous methanol and stirred until homogeneous. Then, 0.8805 g of 1,2-epoxybutane was added dropwise and stirred for 45 minutes to ensure complete reaction and form a homogeneous impregnation solution. Next, 1.00 g of calcined SCM-1 molecular sieve powder (same as in Example 1) was added and stirred until completely dispersed. The mixture was then continuously stirred in air at 20°C for 32 hours. After completion, the mixture was placed in a vacuum drying oven at 50°C and kept under vacuum for 6 hours to obtain the MWW molecular sieve composite material. The methanol extracted during vacuum drying can be recovered and reused as the solvent for the impregnation solution of this invention.

[0042] Example 3

[0043] 1.00 g of polyethyleneimine (99 wt% purity, average molecular weight 1800) was dissolved in 5 g of anhydrous methanol and 1 g of anhydrous ethanol, and stirred until homogeneous. Then, 0.350 g of 1,2-epoxybutane was added dropwise, and the mixture was stirred for 90 minutes to ensure complete reaction and form a homogeneous impregnation solution. Then, calcined SCM-6 molecular sieve powder (prepared according to Example 1 of CN105217651B, with a specific surface area of ​​394 m²) was added. 2 1.00 g of the product was stirred to ensure complete dispersion and continuously stirred in air at 30–35°C for 12 hours. After completion, the product was placed in a vacuum drying oven at 50°C and kept under vacuum for 8 hours to obtain the MWW molecular sieve composite material. The solvent extracted under vacuum can be recycled and reused as the solvent for the impregnation solution of this invention.

[0044] Example 4

[0045] 1.00 g of polyethyleneimine (99 wt% purity, average molecular weight 1800) was dissolved in 6 g of anhydrous methanol and 3 g of anhydrous ethanol, and stirred until homogeneous. Then, 0.650 g of 1,2-epoxybutane and 0.150 g of propylene oxide were added dropwise, and the mixture was stirred for 40 minutes to ensure complete reaction and form a homogeneous impregnation solution. Then, 0.50 g of calcined molecular sieve SCM-1 powder (same as in Example 1) and 0.50 g of SCM-6 powder (same as in Example 3) were added, and the mixture was stirred until completely dispersed and continuously stirred in air at 25–30°C for 18 hours. After completion, the mixture was placed in a vacuum drying oven at 60°C and kept under vacuum for 8 hours to obtain the MWW molecular sieve composite material. The solvent extracted during vacuum extraction can be recovered and reused as the solvent for the impregnation solution of this invention.

[0046] Example 5

[0047] 3.00 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 16 g of anhydrous methanol and stirred until homogeneous. Then, 1.761 g of 1,2-epoxybutane was added dropwise and stirred for 120 minutes to ensure complete reaction and form a homogeneous impregnation solution. Next, 2.00 g of calcined SCM-1 molecular sieve powder (same as in Example 1) was added and stirred until completely dispersed. The mixture was then continuously stirred in air at 20°C for 32 hours. After completion, the product was placed in a vacuum drying oven at 60°C and kept under vacuum for 9 hours to obtain the MWW molecular sieve composite material. The solvent extracted during vacuum drying can be recovered and reused as the solvent for the impregnation solution of this invention.

[0048] Example 6

[0049] 2.00 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 15 g of anhydrous methanol and stirred until homogeneous. Then, 1.174 g of 1,2-epoxybutane was added dropwise and stirred for 50 minutes to ensure complete reaction and form a homogeneous impregnation solution. Next, 2.00 g of calcined SCM-1 molecular sieve powder (same as in Example 1) was added and stirred until completely dispersed. The mixture was then continuously stirred in air at 30°C for 48 hours. After completion, the product was placed in a vacuum drying oven at 60°C and kept under vacuum for 18 hours to obtain the MWW molecular sieve composite material. The solvent extracted during vacuum drying can be recovered and reused as the solvent for the impregnation solution of this invention.

[0050] Example 7

[0051] 0.6667 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 5 g of anhydrous methanol and 3 g of isopropanol, stirred until homogeneous, and then 0.391 g of 1,2-epoxybutane was added dropwise. The mixture was stirred for 75 minutes to ensure complete reaction and form a homogeneous impregnation solution. Then, calcined MCM-22 molecular sieve powder (preparation method as described in the literature, Chinese Journal of Catalysis, 2020, 41, 1062-1066, specific surface area 450 m²) was added. 2 1.00 g ( / g) was stirred to ensure complete dispersion and continuously stirred in air at 30°C for 24 hours. After completion, the product was placed in a vacuum drying oven at 60°C and kept under vacuum for 18 hours to obtain the MWW molecular sieve composite material. The solvent extracted under vacuum can be recycled and reused as the solvent for the impregnation solution of this invention.

[0052] Example 8

[0053] 1.00 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 6 g of anhydrous methanol and stirred until homogeneous. Then, 0.2556 g of propylene oxide was added dropwise and stirred for 60 minutes to ensure complete reaction and form a homogeneous impregnation solution. Next, 1.00 g of calcined SCM-1 molecular sieve powder (same as in Example 1) was added and stirred until completely dispersed. The mixture was then continuously stirred in air at 25°C for 24 hours. After completion, the mixture was placed in a vacuum drying oven at 50°C and kept under vacuum for 5 hours to obtain the MWW molecular sieve composite material. The methanol extracted during vacuum drying can be recovered and reused as the solvent for the impregnation solution of this invention.

[0054] Example 9

[0055] 0.6667 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 5 g of anhydrous methanol and 3 g of isopropanol, stirred until homogeneous, and then 0.391 g of 1,2-epoxybutane was added dropwise. The mixture was stirred for 75 minutes to ensure complete reaction and form a homogeneous impregnation solution. Then, calcined MCM-49 molecular sieve powder (preparation method as described in the literature, Chinese Journal of Catalysis, 2020, 41, 1062-1066, specific surface area 450 m²) was added. 2 1.00 g ( / g) was stirred to ensure complete dispersion and continuously stirred in air at 30°C for 24 hours. After completion, the product was placed in a vacuum drying oven at 60°C and kept under vacuum for 18 hours to obtain the MWW molecular sieve composite material. The solvent extracted under vacuum can be recycled and reused as the solvent for the impregnation solution of this invention.

[0056] Comparative Example 1

[0057] Except that the carrier used for impregnation is 1.00 g of porous silica, the rest is the same as in Example 1.

[0058] Porous silica was prepared using the following method: 900 g of water, 95 g of silica aerogel, and 5 g of 30 wt% silica sol were mixed and stirred until homogeneous. The mixture was then ground using a colloid mill and used as a spray-drying sample. The injection rate was 30 mL / min, the inlet temperature was 210 °C, and the crude porous silica product was obtained by spray drying. This crude product was then calcined at 550 °C to obtain porous silica.

[0059] Comparative Example 2

[0060] Except that the carrier used for impregnation is 1.00 g of porous silica, the rest is the same as in Example 2.

[0061] The preparation method of porous silica is the same as that of Comparative Example 1.

[0062] Comparative Example 3

[0063] 1.00 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 6 g of anhydrous methanol and stirred until homogeneous. Then, 1.00 g of calcined SCM-1 molecular sieve powder (same as in Example 1) was added and stirred until completely dispersed. The mixture was then continuously stirred in air at 25°C for 24 hours. After completion, the mixture was placed in a vacuum drying oven at 50°C and kept under vacuum for 5 hours to obtain the MWW molecular sieve composite material.

[0064] Comparative Example 4

[0065] 0.6667 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 5 g of anhydrous methanol and 3 g of isopropanol, and stirred until homogeneous to form a uniform impregnation solution. Then, 1.00 g of calcined MCM-22 molecular sieve powder (same as in Example 7) was added, stirred until completely dispersed, and continuously stirred in air at 30°C for 24 hours. After completion, the product was placed in a vacuum drying oven at 60°C and kept under vacuum for 18 hours to obtain the MWW molecular sieve composite material. The solvent extracted during vacuum drying can be recovered and reused as the solvent for the impregnation solution of this invention.

[0066] Comparative Example 5

[0067] 0.6667 g of polyethyleneimine (99 wt% purity, average molecular weight 600) was dissolved in 5 g of anhydrous methanol and 3 g of isopropanol, and stirred until homogeneous to form a uniform impregnation solution. Then, 1.00 g of calcined MCM-49 molecular sieve powder (same as in Example 9) was added, stirred until completely dispersed, and continuously stirred in air at 30°C for 24 hours. After completion, the product was placed in a vacuum drying oven at 60°C and kept under vacuum for 18 hours to obtain the MWW molecular sieve composite material. The solvent extracted during vacuum drying can be recovered and reused as the solvent for the impregnation solution of this invention.

[0068] Table 1 shows the composition and adsorption results of the composite materials obtained in each example.

[0069]

[0070]

[0071] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A supported MWW molecular sieve composite material, comprising MWW molecular sieve and epoxy-modified polyethyleneimine supported thereon, wherein, based on the mass of the composite material, the content of the epoxy compound is 0.5%~28.0%, the content of the polyethyleneimine is 5.0%~48.0%, and the mass content of the MWW molecular sieve is 24.0%~90.0%; wherein the epoxy compound is one or two of propylene oxide and 1,2-epoxybutane; The MWW molecular sieve includes at least one of SCM-1, SCM-2, SCM-6, and MCM-49.

2. The composite material according to claim 1, characterized in that, Based on the mass of the composite material, the content of epoxy compound is 10.0%~28.0%, and the content of polyethyleneimine is 25.0%~45.0%.

3. The composite material according to claim 1, characterized in that, The supported MWW molecular sieve composite material has an MWW molecular sieve content of 25.0% to 55.0% based on the mass of the composite material.

4. The composite material according to claim 1, characterized in that, The specific surface area of ​​the MWW molecular sieve is 30~1000 square meters / gram.

5. The composite material according to claim 1, characterized in that, The specific surface area of ​​the MWW molecular sieve is 300~700 square meters / gram.

6. The composite material according to claim 1, characterized in that, The average molecular weight of the polyethyleneimine is 300~100000.

7. The composite material according to claim 1, characterized in that, The average molecular weight of the polyethyleneimine is 500-10000.

8. A method for preparing the composite material according to any one of claims 1-7, comprising: Using MWW molecular sieve material as a carrier, epoxy-modified polyethyleneimine is loaded onto the carrier and dried to obtain a composite material.

9. The preparation method according to claim 8, characterized in that, The method for loading epoxy-modified polyethyleneimine onto the carrier is an impregnation method, wherein the impregnation solution for epoxy-modified polyethyleneimine is prepared by: dissolving polyethyleneimine in a solvent to prepare an impregnation solution, then adding an epoxy compound dropwise, and stirring for 10 to 480 minutes to obtain the impregnation solution.

10. The preparation method according to claim 9, characterized in that, Polyethyleneimine is dissolved in a solvent to prepare an impregnation solution, and then an epoxy compound is added dropwise. The mixture is stirred for 30 to 300 minutes to obtain the impregnation solution.

11. The preparation method according to claim 9, characterized in that, The impregnation solution contains epoxy compounds and polyethyleneimine at mass concentrations of 0.05% to 36%.

12. The preparation method according to claim 11, characterized in that, The impregnation solution contains 1% to 25% by mass of epoxy compound and polyethyleneimine.

13. The preparation method according to claim 9, characterized in that, The immersion temperature is 1~50 °C.

14. The preparation method according to claim 13, characterized in that, The immersion temperature is 15~40 °C.

15. The preparation method according to claim 13, characterized in that, The impregnation temperature is 20~30 °C.

16. The preparation method according to claim 9, characterized in that, The soaking time is 3 to 120 hours.

17. The preparation method according to claim 16, characterized in that, The soaking time is 6 to 72 hours.

18. The preparation method according to claim 8, characterized in that, The drying process employs vacuum heating at a temperature of 40-150 °C for a duration of 2-50 hours.

19. The preparation method according to claim 18, characterized in that, The drying process employs vacuum heating at a temperature of 50–130 °C for a duration of 3–24 h.

20. The use of the composite material according to any one of claims 1-7 in carbon dioxide adsorption.

21. The application according to claim 20, characterized in that, The application includes: contacting a carbon dioxide-containing gas with the composite material to obtain a purified gas; wherein the carbon dioxide-containing gas has a volume content of 0.04% to 60%, and other gases include at least one of nitrogen, methane, carbon monoxide, and hydrogen.

22. The application according to claim 20 or 21, characterized in that, The adsorption conditions are as follows: temperature 10–85 °C, pressure 0.01–100 kPa, time 1–60 min, and volumetric hourly space velocity 5–2400 h⁻¹. -1 .

23. The application according to claim 22, characterized in that, The adsorption conditions are as follows: temperature 40~75 °C.

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