Carbon-based molecular sieve and 13X zeolite prepared from coal gangue, preparation method and application

Abstract

The present invention provides a carbon-based molecular sieve and 13X zeolite prepared from coal gangue, a preparation method, and applications. The method uses coal gangue as raw material, grinds, carbonizes, activates, and deposits to obtain a carbon-based molecular sieve and an activated silicon phase, and then chemically excites and hydrothermally seed-induces the obtained silicon-aluminum phase to obtain the 13X zeolite. The method of the present invention fully utilizes the main phases of coal gangue and reduces waste emissions from the process. The carbon-based molecular sieve and 13X zeolite ultimately prepared by the present invention both have high specific surface areas and micropore volumes. The carbon-based molecular sieve has nitrogen selectivity and can be used in a fixed-bed separation device to purify nitrogen with a purity exceeding 99.9% from flue gas. The obtained 13X zeolite has carbon dioxide selectivity and can be used in a fixed-bed separation device to purify carbon dioxide with a purity exceeding 99.9% from flue gas.

Description

Technical Field

[0001] The present invention belongs to the field of materials and relates to the preparation of molecular sieves and zeolites, and in particular to a carbon-based molecular sieve and 13X zeolite prepared from coal gangue, a preparation method and applications. Background Art

[0002] CO2 is one of the most important causes of global warming. Climate change caused by greenhouse gases has seriously threatened our living environment, and greenhouse gas emissions reduction is urgent. In recent years, the development of carbon capture, utilization, and storage technologies has made it possible to reduce the greenhouse gas CO2. Since CO2 capture can effectively separate and concentrate CO2 without changing existing facilities and processes, CO2 capture has become an effective measure to reduce CO2 in the flue gas of coal-fired power plants. Pressure swing adsorption is a physical gas adsorption separation technology with low production costs, simple operation, and high product purity. It has been widely promoted and applied in industry. In the pressure swing adsorption process, molecular sieves are the core component and determine the actual effect of the separation process. Porous carbon-based molecular sieves and 13X zeolite, with their excellent molecular pores, can effectively separate nitrogen or carbon dioxide from flue gas under low temperature and low pressure conditions.

[0003] Aluminates and silicates can both be used as aluminum and silicon sources for the synthesis of 13X zeolite, but these raw materials are chemical products and are relatively expensive. Coal gangue, a solid waste, is readily available and inexpensive. Furthermore, it is rich in carbon, organic matter, and silicon-aluminum phases. Using coal gangue as a raw material to produce carbon-based molecular sieves and 13X zeolite could yield significant environmental and economic benefits. However, the existing technology lacks mature technologies for preparing carbon-based molecular sieves and 13X zeolite from coal gangue. Summary of the Invention

[0004] In view of the defects and shortcomings of the existing technology, the purpose of the present invention is to provide a carbon-based molecular sieve and 13X zeolite prepared using coal gangue, a preparation method and application.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A method for preparing carbon-based molecular sieves and 13X zeolite using coal gangue. The method uses coal gangue as raw material, grinds, carbonizes, activates, and deposits to obtain carbon-based molecular sieves and activated silicon phases, and then chemically excites and hydrothermally seed-induces the obtained silicon-aluminum phases to obtain 13X zeolite.

[0007] The present invention also has the following technical features:

[0008] Specifically, the method includes the following steps:

[0009] Step 1: ball-milling coal gangue to obtain coal gangue powder, and then placing the coal gangue powder in a rotary kiln for carbonization, activation and deposition to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase mixture;

[0010] Step 2: Separating the carbon-based molecular sieve and activated silicon-aluminum phase mixture obtained in step 1 in a flotation machine to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase;

[0011] Step 3: Mix the activated silicon-alumina phase separated in step 2 with a formulated amount of water, water glass, sodium hydroxide and 13X zeolite seed crystals to obtain a mixed liquid A; place the mixed liquid A in a hydrothermal kettle for a hydrothermal reaction to obtain a mixed liquid B; and filter and dry the mixed liquid B to obtain 13X zeolite.

[0012] Furthermore, the carbonization temperature in step 1 is 750-790°C, the carbonization heating rate is 5-15°C / min, the activation temperature is 790-830°C, the activation aid is water vapor, the activation time is 30-60min, the deposition temperature is 710-750°C, the deposition aid is nitrogen, and the deposition time is 90-120min.

[0013] Furthermore, in step 3, the activated silicon-alumina phase is 30.3-35.7%, water is 45.5-50.9%, water glass is 10.9-15.2%, sodium hydroxide is 5.9-9.7% and 13X zeolite seed crystals are 0.5-1.1%, and the total mass percentage of each component is 100%.

[0014] Furthermore, in step 3, the hydrothermal reaction temperature is 80-100°C, the hydrothermal reaction time is 60-120 minutes, and the drying temperature is 60°C.

[0015] Furthermore, the method comprises the following steps:

[0016] Step 1, ball milling the coal gangue to obtain 200-mesh coal gangue powder, then placing the coal gangue powder in a rotary kiln, heating it to 780°C at 10°C / min for carbonization, then heating it to 800°C, using water vapor as an activation aid for activation, and the activation time is 30 minutes to obtain activated coal gangue, and then using nitrogen as a deposition aid, depositing at a deposition temperature of 720°C for 90 minutes to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase mixture;

[0017] Step 2: Separating the carbon-based molecular sieve and activated silicon-aluminum phase mixture obtained in step 1 in a flotation machine to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase;

[0018] Step 3: Mixing the activated silicon-alumina phase separated in step 2 with a formulated amount of water, water glass, sodium hydroxide, and 13X zeolite seed crystals to obtain a mixed liquid A; placing the mixed liquid A in a hydrothermal kettle for hydrothermal reaction to obtain a mixed liquid B; filtering and drying the mixed liquid B to obtain 13X zeolite;

[0019] Among them, the mixed liquid A includes the following raw material components, calculated by mass percentage, 30.7% activated silica-alumina phase, 48.9% water, 13.2% water glass, 6.6% sodium hydroxide and 0.6% 13X zeolite seeds; the hydrothermal temperature is 80°C, the hydrothermal time is 120 minutes, and the drying temperature is 60°C.

[0020] Furthermore, the specific surface area of ​​the carbon-based molecular sieve is 365m 2 / g, and the micropore volume is 0.159cm 3 / g; the specific surface area of ​​the 13X zeolite is 579m 2 / g, and the micropore volume is 0.249cm 3 / g.

[0021] The present invention also protects the carbon-based molecular sieve and 13X zeolite prepared by the above method.

[0022] The present invention also protects the use of the carbon-based molecular sieve and 13X zeolite prepared by the above method for preparing a fixed bed separation device, which is used to enrich nitrogen and carbon dioxide from flue gas.

[0023] Furthermore, the formulated amount of carbon-based molecular sieve, phenolic resin and polyethylene glycol is placed in an extruder and pressed to form a nitrogen adsorption layer, and the formulated amount of 13X zeolite powder, phenolic resin and polyethylene glycol is placed in an extruder and pressed to form a carbon dioxide adsorption layer, and then the obtained carbon dioxide adsorption layer is filled into the bottom of the fixed bed separation device, and the nitrogen adsorption layer is filled above the carbon dioxide adsorption layer in the fixed bed separation device;

[0024] In which, by mass percentage, the carbon-based molecular sieve or 13X zeolite powder is 85.3%, the phenolic resin is 14.4% and the polyethylene glycol is 0.3%.

[0025] Compared with the prior art, the present invention has the following beneficial technical effects:

[0026] (I) The method of the present invention uses coal gangue as raw material to prepare carbon-based molecular sieves and 13X zeolite. The obtained carbon-based molecular sieves and 13X zeolite both have high specific surface area and micropore volume. The carbon-based molecular sieve has nitrogen selectivity and can be used in a fixed-bed separation device to purify nitrogen with a purity exceeding 99.9% from flue gas. The obtained 13X zeolite has carbon dioxide selectivity and can be used in a fixed-bed separation device to purify carbon dioxide with a purity exceeding 99.9% from flue gas.

[0027] (II) The preparation method of the present invention uses coal gangue as the main raw material, converts the carbon, organic matter and other components contained in the coal gangue into a carbon-based molecular sieve, and converts the residual silicon-aluminum phase into 13X zeolite, thereby fully utilizing the main phase of the coal gangue and reducing waste emissions in the process.

[0028] (III) The carbon-based molecular sieve and 13X zeolite prepared by the method of the present invention can be filled into a fixed-bed separation device to enrich nitrogen and carbon dioxide from flue gas, thus realizing the environmental protection concept of treating waste with waste. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The XRD pattern of 13X zeolite prepared in Example 1 is shown below:

[0030] Figure 2 Pore ​​size distribution diagram of the carbon-based molecular sieve prepared in the embodiment;

[0031] Figure 3 Pore ​​size distribution diagram of 13X zeolite prepared in the examples;

[0032] Figure 4 It is a structural schematic diagram of a fixed bed separation device in an embodiment of the present invention.

[0033] The numbers in the figure represent:

[0034] 1-Flue gas inlet, 2-vortex air flow distributor, 3-carbon dioxide adsorption layer, 4-nitrogen adsorption layer, 5-brown pressure pad, 6-compensation type automatic pressing device, 7-gas outlet.

[0035] The technical solution of the present invention is further described below in conjunction with embodiments. DETAILED DESCRIPTION

[0036] The present invention provides a method for preparing carbon-based molecular sieves and 13X zeolite by using coal gangue. The method uses coal gangue as raw material, grinds, carbonizes, activates and deposits to obtain carbon-based molecular sieves and activated silicon phases, and then chemically excites and hydrothermally seed-induces the obtained silicon-aluminum phases to obtain 13X zeolite.

[0037] The coal gangue used in the present invention includes the following raw material components, calculated by mass percentage, SiO2 45.1-58.3%, Al2O3 14.2-30.7%, Fe2O3 1.4-8.1%, CaO 0.7-4.7%, MgO 0.5-1.3%, K2O2.1-2.9%, TiO2 0.4-0.9%, carbon, organic matter and other trace components 10.5-12.5%, and the mass percentages of each component add up to 100%.

[0038] Preferably, the method comprises the following steps:

[0039] Step 1: ball-milling coal gangue to obtain coal gangue powder, and then placing the coal gangue powder in a rotary kiln for carbonization, activation and deposition to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase mixture;

[0040] Step 2: Separating the carbon-based molecular sieve and activated silicon-aluminum phase mixture obtained in step 1 in a flotation machine to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase;

[0041] Step 3: Mix the activated silicon-alumina phase separated in step 2 with a formulated amount of water, water glass, sodium hydroxide and 13X zeolite seed crystals to obtain a mixed liquid A; place the mixed liquid A in a hydrothermal kettle for a hydrothermal reaction to obtain a mixed liquid B; and filter and dry the mixed liquid B to obtain 13X zeolite.

[0042] Preferably, the carbonization temperature in step 1 is 750-790°C, the carbonization heating rate is 5-15°C / min, the activation temperature is 790-830°C, the activation aid is water vapor, the activation time is 30-60 min, the deposition temperature is 710-750°C, the deposition aid is nitrogen, and the deposition time is 90-120 min.

[0043] Preferably, in step 3, the activated silicon-alumina phase is 30.3-35.7%, water is 45.5-50.9%, water glass is 10.9-15.2%, sodium hydroxide is 5.9-9.7% and 13X zeolite seed crystals are 0.5-1.1%, and the total mass percentage of each component is 100%.

[0044] Preferably, in step 3, the hydrothermal reaction temperature is 80-100°C, the hydrothermal reaction time is 60-120 minutes, and the drying temperature is 60°C.

[0045] In accordance with the above technical solution, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solution of this application fall within the protection scope of the present invention.

[0046] Example 1

[0047] This embodiment discloses a method for preparing carbon-based molecular sieves and 13X zeolite using coal gangue, comprising the following steps:

[0048] Specifically, the method includes the following steps:

[0049] Step 1, ball milling the coal gangue to obtain 200-mesh coal gangue powder, then placing the coal gangue powder in a rotary kiln, heating it to 780°C at 10°C / min for carbonization, then heating it to 800°C, using water vapor as an activation aid for activation, and the activation time is 30 minutes to obtain activated coal gangue, and then using nitrogen as a deposition aid, depositing at a deposition temperature of 720°C for 90 minutes to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase mixture;

[0050] Step 2: Separating the carbon-based molecular sieve and activated silicon-aluminum phase mixture obtained in step 1 in a flotation machine to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase;

[0051] Step 3: Mixing the activated silicon-alumina phase separated in step 2 with a formulated amount of water, water glass, sodium hydroxide, and 13X zeolite seed crystals to obtain a mixed liquid A; placing the mixed liquid A in a hydrothermal kettle for hydrothermal reaction to obtain a mixed liquid B; filtering and drying the mixed liquid B to obtain 13X zeolite;

[0052] Among them, the mixed liquid A includes the following raw material components, calculated by mass percentage, 30.7% activated silica-alumina phase, 48.9% water, 13.2% water glass, 6.6% sodium hydroxide and 0.6% 13X zeolite seeds; the hydrothermal temperature is 80°C, the hydrothermal time is 120 minutes, and the drying temperature is 60°C, wherein water glass and sodium hydroxide are activators, and 13X zeolite is used as zeolite seeds.

[0053] The XRD crystal phase analysis of the 13X zeolite prepared in this example is as follows: Figure 1 The pore structure distribution of carbon-based molecular sieve and 13X zeolite is shown in Figure 3; the output of carbon-based molecular sieve, output of 13X zeolite, specific surface area and micropore volume are shown in Table 1; the flue gas separation efficiency and adsorption capacity of carbon-based molecular sieve and 13X zeolite are shown in Table 2.

[0054] The carbon-based molecular sieve and 13X zeolite prepared in this example were filled in Figure 1 In the fixed bed separation device shown, a flue gas separation test is carried out, specifically including:

[0055] In terms of mass percentage, 85.3% of carbon-based molecular sieve, 14.4% of phenolic resin and 0.3% of polyethylene glycol were placed in an extruder and pressed to form a nitrogen adsorption layer; the formulated amount of 13X zeolite powder, phenolic resin and polyethylene glycol were placed in an extruder and pressed to form a carbon dioxide adsorption layer, and then the obtained carbon dioxide adsorption layer was filled into the following manner: Figure 4At the bottom of the fixed bed separation device shown, the nitrogen adsorption layer is filled above the carbon dioxide adsorption layer in the fixed bed separation device, that is, the nitrogen adsorption layer is filled to the middle or upper part of the fixed bed separation device, and then the fixed bed separation device is used to perform a flue gas separation test.

[0056] In the flue gas separation test, nitrogen was introduced from the bottom of the fixed bed separation device at a flow rate of 50 ml / min for purging to remove the air in the fixed bed separation device, and then flue gas was introduced at a flow rate of 50 mL / min to start flue gas separation. The pressure was maintained at 101.325 kPa during the flue gas separation process.

[0057] A breakthrough curve was constructed by plotting the ratio of the outlet gas concentration at the interval (Ct) to the outlet gas concentration at equilibrium (C0) as a function of time. The total adsorption capacity of the carbon-based molecular sieve and 13X zeolite was determined by CO2 adsorption accumulation. A gas chromatograph with a thermal conductivity detector was installed at the outlet of the fixed-bed separation device to monitor the gas phase composition at the outlet of the fixed-bed separation device, thereby determining the separation concentration of the material for the mixed gas. The test results are shown in Tables 1 and 2.

[0058] Example 2

[0059] This embodiment discloses a method for preparing carbon-based molecular sieves and 13X zeolite using coal gangue. The preparation steps and raw material components are the same as those in Example 1, except that the carbonization temperature is 770°C, the activation temperature is 810°C, and the deposition temperature is 730°C.

[0060] The pore structure distribution of the carbon-based molecular sieve and 13X zeolite prepared in this example is shown in Figure 3, and the carbon-based molecular sieve yield, 13X zeolite yield, specific surface area, and micropore volume are shown in Table 1. The flue gas separation efficiency and adsorption capacity of the carbon-based molecular sieve and 13X zeolite are shown in Table 2.

[0061] Example 3

[0062] This embodiment discloses a method for preparing carbon-based molecular sieves and 13X zeolite using coal gangue. The preparation steps and raw material components are the same as those in Example 1, except that: in step 1, the carbonization temperature is 790°C, the activation temperature is 830°C, and the deposition temperature is 750°C.

[0063] The pore structure distribution of the carbon-based molecular sieve and 13X zeolite prepared in this example is shown in Figure 3, and the carbon-based molecular sieve yield, 13X zeolite yield, specific surface area, and micropore volume are shown in Table 1. The flue gas separation efficiency and adsorption capacity of the carbon-based molecular sieve and 13X zeolite are shown in Table 2.

[0064] Example 4

[0065] This embodiment discloses a method for preparing a carbon-based molecular sieve and 13X zeolite using coal gangue. The preparation steps and raw material components are the same as those in Example 1, except that: in step 3, the mass percentages of activated silica-alumina phase, water, water glass, sodium hydroxide and 13X zeolite seed crystals are 30.7%, 48.9%, 13.2%, 6.6% and 0.6% respectively.

[0066] The pore structure distribution of the carbon-based molecular sieve and 13X zeolite prepared in this example is shown in Figure 3, and the carbon-based molecular sieve yield, 13X zeolite yield, specific surface area, and micropore volume are shown in Table 1. The flue gas separation efficiency and adsorption capacity of the carbon-based molecular sieve and 13X zeolite are shown in Table 2.

[0067] Comparative Example 1

[0068] This comparative example uses the common commercial PSA nitrogen and carbon dioxide-based molecular sieves, whose main components are also 13X zeolite and carbon-based molecular sieves. The difference is that the preparation raw materials and processes used are different. The carbon-based molecular sieve and 13X zeolite of the present invention are compared with them to reflect the advantages of the present invention.

[0069] The specific surface area and micropore volume of the nitrogen and carbon dioxide-producing molecular sieves in Comparative Example 1 are shown in Table 1, and the flue gas separation efficiency and adsorption capacity are shown in Table 2.

[0070] Table 1. Carbon-based molecular sieve production, 13X zeolite production, specific surface area, and micropore volume

[0071]

[0072] Table 2. Flue gas separation efficiency and adsorption capacity of carbon-based molecular sieves and 13X zeolite

[0073]

[0074]

[0075] Combining the data in the above table with Figure 2 、 Figure 3, it can be seen that the two substances prepared in Examples 1 to 4 are carbon-based molecular sieves and 13X zeolite, respectively. The quantitative analysis results show that the carbonization, activation and deposition temperatures will not only affect the production of carbon-based molecular sieves, but also the production of 13X zeolite. This is because excessively high temperatures will not only slow down the efficiency of carbonization, activation and deposition, but will also cause the silicon-aluminum phase in the gangue to be over-fired and inactivated, making it impossible to depolymerize and reconstruct it into 13X zeolite under the action of an alkaline activator. The specific surface area and micropore volume-based flue gas separation efficiency of carbon-based molecular sieves and 13X zeolites with different yields are basically the same, which shows that changing the process conditions only affects the production of the product. Under the same carbonization, activation and deposition process conditions, significantly increasing the concentration of the alkaline activator cannot significantly change the yield of 13X zeolite, so the alkaline activator has little effect on the production of 13X zeolite.

[0076] The above analysis results show that the two substances obtained in Examples 1 to 4, namely carbon-based molecular sieve and 13X zeolite, have better specific surface area, micropore volume and flue gas separation efficiency in a fixed bed separation device than commercial products under the same conditions.

[0077] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings. However, the present disclosure is not limited to the specific details of the above embodiments. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the scope of protection of the present disclosure.

[0078] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present disclosure will not further describe various possible combinations. In addition, the various different embodiments of the present disclosure can also be arbitrarily combined, as long as they do not violate the concept of the present disclosure, and they should also be regarded as the content disclosed by the present disclosure.

Claims

1. A method for preparing carbon-based molecular sieves and 13X zeolite using coal gangue, characterized in that: The method uses coal gangue as raw material, obtains carbon-based molecular sieve and activated silicon phase through grinding, carbonization, activation and deposition, and then chemically excites and hydrothermally seed-induces the obtained silicon-aluminum phase to obtain 13X zeolite. The method comprises the following steps: Step 1: ball-milling coal gangue to obtain coal gangue powder, and then placing the coal gangue powder in a rotary kiln for carbonization, activation and deposition to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase mixture; Step 2: Separating the carbon-based molecular sieve and activated silicon-aluminum phase mixture obtained in step 1 in a flotation machine to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase; Step 3: Mixing the activated silicon-alumina phase separated in step 2 with a formulated amount of water, water glass, sodium hydroxide, and 13X zeolite seed crystals to obtain a mixed liquid A; placing the mixed liquid A in a hydrothermal kettle for hydrothermal reaction to obtain a mixed liquid B; filtering and drying the mixed liquid B to obtain 13X zeolite; The carbonization temperature in step 1 is 750-790°C, the carbonization heating rate is 5-15°C / min, the activation temperature is 790-830°C, the activation aid is water vapor, the activation time is 30-60 min, the deposition temperature is 710-750°C, the deposition aid is nitrogen, and the deposition time is 90-120 min; In step 3, the activated silicon-alumina phase comprises 30.3-35.7% of activated silicon-alumina phase, 45.5-50.9% of water, 10.9-15.2% of water glass, 5.9-9.7% of sodium hydroxide and 0.5-1.1% of 13X zeolite seed crystals, and the total mass percentage of each component is 100%.

2. The method according to claim 1, wherein: In step 3, the hydrothermal reaction temperature is 80-100° C., the hydrothermal reaction time is 60-120 min, and the drying temperature is 60° C.

3. The method according to claim 1, wherein: The method comprises the following steps: Step 1, ball-milling the coal gangue to obtain 200-mesh coal gangue powder, then placing the coal gangue powder in a rotary kiln, heating it to 780°C at 10°C / min for carbonization, then heating it to 800°C, activating it with water vapor as an activation aid for 30 minutes to obtain activated coal gangue, and then using nitrogen as a deposition aid to deposit it at a deposition temperature of 720°C for 90 minutes to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase mixture; Step 2: Separating the carbon-based molecular sieve and activated silicon-aluminum phase mixture obtained in step 1 in a flotation machine to obtain a carbon-based molecular sieve and an activated silicon-aluminum phase; Step 3: Mixing the activated silicon-alumina phase separated in step 2 with a formulated amount of water, water glass, sodium hydroxide, and 13X zeolite seed crystals to obtain a mixed liquid A; placing the mixed liquid A in a hydrothermal kettle for hydrothermal reaction to obtain a mixed liquid B; filtering and drying the mixed liquid B to obtain 13X zeolite; Among them, the mixed liquid A includes the following raw material components, calculated by mass percentage, 30.7% activated silica-alumina phase, 48.9% water, 13.2% water glass, 6.6% sodium hydroxide and 0.6% 13X zeolite seeds; the hydrothermal temperature is 80°C, the hydrothermal time is 120 minutes, and the drying temperature is 60°C.

4. The method according to claim 1, wherein: The specific surface area of ​​the carbon-based molecular sieve is 365m 2 / g, and the micropore volume is 0.159cm 3 / g; the specific surface area of ​​the 13X zeolite is 579m 2 / g, and the micropore volume is 0.249cm 3 / g.

5. Use of the carbon-based molecular sieve and 13X zeolite prepared by the method according to any one of claims 1 to 4 in preparing a fixed-bed separation device for enriching nitrogen and carbon dioxide from flue gas.

6. The use according to claim 5, characterized in that The carbon-based molecular sieve, phenolic resin and polyethylene glycol in a formula amount are placed in an extruder for compression molding to obtain a nitrogen adsorption layer, and the 13X zeolite powder, phenolic resin and polyethylene glycol in a formula amount are placed in an extruder for compression molding to obtain a carbon dioxide adsorption layer, and then the obtained carbon dioxide adsorption layer is filled into the bottom of a fixed bed separation device, and the nitrogen adsorption layer is filled into the upper part of the carbon dioxide adsorption layer in the fixed bed separation device; In which, by mass percentage, the carbon-based molecular sieve or 13X zeolite powder is 85.3%, the phenolic resin is 14.4% and the polyethylene glycol is 0.3%.

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