Method for preparing CMS carbon molecular sieve based on phenolic resin foam material

Abstract

The invention belongs to the technical field of molecular sieves, and particularly provides a method for preparing a CMS carbon molecular sieve based on a phenolic resin foaming material. A method for preparing a CMS carbon molecular sieve based on a phenolic resin foaming material.The method comprises the following steps of 1, smashing phenolic resin, conducting primary drying, grinding and then conducting secondary drying to obtain resin powder, and 2, mixing the resin powder, a pore forming agent and auxiliaries, conducting extrusion forming, carbonizing and depositing to obtain the CMS carbon molecular sieve.The prepared CMS carbon molecular sieve has the advantage of being high in anti-pressure ability.

Description

Technical Field

[0001] This application belongs to the field of molecular sieve technology, and in particular relates to a method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials. Background Technology

[0002] Carbon molecular sieves, as porous carbon materials with precise pore size distribution, demonstrate high value in the field of gas separation. Their separation performance and structural stability directly determine their application efficiency, while compressive strength and nitrogen yield are key indicators for evaluating their industrial applicability. In gas separation, carbon molecular sieves need to achieve selective adsorption and diffusion of gas molecules under certain pressure conditions. Excellent compressive strength can prevent material breakage or structural collapse during loading and operation, ensuring the long-term stable operation of the separation system. Simultaneously, high nitrogen yield can improve the nitrogen production efficiency per unit time, meeting the large-scale, continuous demand for high-purity nitrogen in fields such as electronics, chemicals, and food preservation. Therefore, optimizing the preparation process of carbon molecular sieves around these two core indicators has become the core direction for promoting their industrial application. Phenolic resins, rich in aromatic rings and hydroxyl groups in their molecular structure, possess unique advantages such as high carbon yield, strong thermal stability, and easily controllable cross-linking structure, making them one of the ideal precursors for preparing high-performance carbon molecular sieves. Compared to traditional coal-based and lignin-based precursors, phenolic resins, during carbonization and activation, can form uniform microporous and mesoporous structures through controllable pyrolysis reactions. This provides ample channels for the rapid transport and selective adsorption of gas molecules, helping to improve the nitrogen production performance of carbon molecular sieves, making phenolic resin-based carbon molecular sieves a current hot research topic. However, current phenolic resin-based carbon molecular sieves still have certain shortcomings in practical applications. A prominent problem is performance degradation due to high-speed collisions during use. During the packing process of carbon molecular sieves, high-speed collisions between particles easily cause surface damage or structural cracks. During operation, the high-speed impact of airflow and pressure changes exacerbate friction and collisions between carbon molecular sieve particles, leading to the breakage of some particles and the generation of dust. These problems not only reduce the packing density of the carbon molecular sieve, affecting gas separation efficiency and nitrogen production, but also cause dust to clog equipment pipelines, shorten equipment lifespan, and increase production and maintenance costs. Therefore, optimizing the preparation process of carbon molecular sieves and improving their resistance to high-speed collisions has become a key issue that urgently needs to be addressed in the research field of phenolic resin-based carbon molecular sieve preparation. Summary of the Invention

[0003] To address the aforementioned issues and further improve the compressive strength and nitrogen production performance of carbon molecular sieves, this application provides a method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials.

[0004] This application provides a method for preparing CMS carbon molecular sieve based on phenolic resin foam material, including the following steps: 1) pulverizing phenolic resin, drying it once, grinding it, and then drying it a second time to obtain resin powder; 2) Mix resin powder, pore-forming agent, and additives, extrude, carbonize, and deposit to obtain CMS carbon molecular sieve.

[0005] Furthermore, in step 1), the phenolic resin includes phenolic resin waste and virgin phenolic resin.

[0006] Furthermore, in step 1), the drying temperature is 150-200℃ and the time is 1.5-2.5h. And / or, the secondary drying temperature is 160-180℃, and the time is 1-2 hours.

[0007] Furthermore, in step 1), the particle size of the resin powder is 5-30 μm.

[0008] Furthermore, in step 2), the pore-forming agent includes starch and chitosan; And / or, the additives include coal tar, bitumen, and water.

[0009] Furthermore, in step 2), carbonization includes a first stage, a second stage, and a third stage; The first stage involves raising the temperature to 300-320℃ at a heating rate of 2-2.5 min / ℃. The second stage involves raising the temperature to 650-670℃ at a heating rate of 4-6 min / ℃. The third stage involves raising the temperature to 850-870℃ at a heating rate of 3.5-6.5 min / ℃.

[0010] Furthermore, in step 2), the specific deposition process is as follows: adjust the temperature to 750-850℃, introduce benzene at a rate of 30-40g / min to adjust the pore size, the dripping time is 25-35min, and after the dripping is completed, keep warm for 2.5-3.5h.

[0011] Furthermore, the additive also includes porous nanotubes; The method for preparing the porous nanotubes includes the following steps: S1: Take water-soluble zinc salt, water-soluble calcium salt, polyvinylpyrrolidone, and solvent, mix them evenly to obtain the precursor solution; S2: Electrospinning the precursor solution to obtain fibers, which are then calcined, pulverized, and sieved to obtain porous nanotubes.

[0012] Furthermore, in step S1, the solvent includes ethanol and N,N-dimethylformamide.

[0013] Furthermore, in step S2, the electrospinning process parameters are: voltage 12-12.5kV, receiving distance 18-19cm.

[0014] Compared with the prior art, this application has the following beneficial effects: 1. By using a mixture of phenolic resin waste and virgin phenolic resin to prepare resin powder, the skeleton formed during carbonization of the resin powder has higher strength and better stability, and the pore structure of the carbon molecular sieve is uniform, which further improves the compressive strength of the carbon molecular sieve, thereby giving the carbon molecular sieve better nitrogen production performance.

[0015] 2. Porous nanotubes can play a supporting role in carbon molecular sieves, preventing them from breaking due to continuous collisions and stress during operation, thus improving their stability. At the same time, due to the difference in ionic radii between zinc and calcium ions, the nanotubes have a fine porous structure on their surface, which facilitates the passage of gas molecules and prevents blockage in the carbon molecular sieve, thereby giving the carbon molecular sieve good nitrogen production performance. Attached Figure Description

[0016] Figure 1 This is a process flow diagram of the method for preparing CMS carbon molecular sieves based on phenolic resin foaming material in Examples 1-5 of this application. Detailed Implementation

[0017] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0019] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only,” “consisting of,” etc., is used, in which case another component may be added.

[0020] The terms "preferred," "more preferably," "better," and "even better" used in this application refer to embodiments of this application that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this application. That is, in this application, "preferred," "more preferably," "better," and "even better" are merely descriptions of implementations or embodiments with better effects, but do not constitute a limitation on the scope of protection of this application.

[0021] In this application, terms such as "further," "even more," and "particularly" are used for descriptive purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0022] In this application, "at least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layered" means at least two layers, such as two layers, three layers, etc., unless otherwise explicitly specified. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0023] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0024] Unless otherwise specified, all steps in this application may be performed sequentially or randomly. For example, the method comprising steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc. Unless otherwise stated, singular terms may include plural forms and should not be construed as having a quantity of one.

[0025] In this application, "above" or "below" includes the number itself. For example, "below 1" includes 1.

[0026] In this application, room temperature refers to 0-40°C, including but not limited to 10-40°C, or further to 20-30°C.

[0027] The present application will be further illustrated by the following examples, but these examples do not limit the scope of the present application.

[0028] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in this application, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. All reagents or instruments whose manufacturers are not specified are conventional products that can be purchased commercially. In addition to the specific methods, equipment, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description in this application, any prior art methods, equipment, and materials similar to or equivalent to those described, used, or made by the methods, equipment, and materials in the embodiments of this application may be used to implement this application.

[0029] The process flow diagrams of the methods for preparing CMS carbon molecular sieves based on phenolic resin foaming materials in Examples 1-5 of this application are as follows: Figure 1 As shown.

[0030] Example 1 The method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials in this embodiment includes the following steps: 1) Weigh phenolic resin waste and phenolic resin virgin material with a moisture content of 10%-15% according to a mass ratio of 1:3. Then, crush them separately using a pulverizer, generating a small amount of dust (G1). The crushed material is then dried once in a dryer, generating a small amount of dust at the end of the dryer (G2). The drying temperature is 150℃ and the time is 2.5h. After the first drying, the material is ball-milled into a fine powder, generating ball milling dust (G3). The fine powder is then dried a second time in a dryer, generating a small amount of dust at the end of the dryer (G4). The drying temperature is 180℃ and the time is 1h, resulting in resin powder with a moisture content of 5% and an average particle size of 5μm. 2) The resin powder, starch, chitosan, coal tar, asphalt and water are mixed and stirred in a mass ratio of 70:4:1:5:3:60. A small amount of dust will be generated during the mixing process (G5). The mixture is then fed into an automatic temperature-controlled kneader. After being kneaded evenly in the kneader, it is then extruded into shape by a twin-screw extruder to obtain the base material. A small amount of fugitive organic waste gas will be volatilized during the discharge process of the kneader (Gu1). 3) The base material enters the cylinder of the carbonization furnace for carbonization. In the first stage, the temperature is raised to 300℃ at a heating rate of 2 min / ℃. In the second stage, the temperature is raised to 650℃ at a heating rate of 6 min / ℃. Finally, in the third stage, the temperature is raised to 840℃ at a heating rate of 3.5 min / ℃. After carbonization, the material enters the deposition furnace for deposition treatment. Under nitrogen protection, the temperature is raised to 750℃, and benzene (pure benzene) is introduced at a rate of 30 g / min for pore adjustment. The addition time is 35 min, and the material is kept at this temperature for 2.5 h after addition. After cooling... The process involves detection and sieving (dust generated during sieving – G6 – is collected using a bag filter; defective products obtained from sieving are returned to the deposition furnace for re-deposition) to obtain the finished product, namely CMS carbon molecular sieve with an average particle size of 1mm. VOCs and other pollutants generated during the carbonization and deposition process (G7) are collected through pipelines and then sent to the main incinerator for combustion, achieving a combustion completion rate of over 90%. The gas then enters the regenerative dust removal chamber, undergoes the first dust removal, and then enters the auxiliary combustion furnace for residual waste gas incineration. After being cooled by water cooling tower, the gas is discharged through a 15m high exhaust stack to meet emission standards (G8).

[0031] Example 2 The method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials in this embodiment includes the following steps: 1) Weigh phenolic resin waste and phenolic resin virgin with a moisture content of 10%-15% according to a mass ratio of 1:3. Then, crush them separately using a pulverizer, generating a small amount of dust (G1). The crushed material is then dried once in a dryer, generating a small amount of dust at the end of the dryer (G2). The drying temperature is 200℃ and the time is 1.5h. After the first drying, the material is ball-milled into a fine powder, generating ball mill dust (G3). The fine powder is then dried a second time in a dryer, generating a small amount of dust at the end of the dryer (G4). The drying temperature is 160℃ and the time is 2h, resulting in resin powder with a moisture content of 8% and an average particle size of 30μm. 2) The resin powder, starch, chitosan, coal tar, asphalt and water are mixed and stirred in a mass ratio of 70:4:1:5:3:60. A small amount of dust will be generated during the mixing process (G5). The mixture is then fed into an automatic temperature-controlled kneader. After being kneaded evenly in the kneader, it is then extruded into shape by a twin-screw extruder to obtain the base material. A small amount of fugitive organic waste gas will be volatilized during the discharge process of the kneader (Gu1). 3) The base material enters the cylinder of the carbonization furnace for carbonization. In the first stage, the temperature is raised to 320℃ at a heating rate of 2.5 min / ℃. In the second stage, the temperature is raised to 670℃ at a heating rate of 4 min / ℃. Finally, in the third stage, the temperature is raised to 850℃ at a heating rate of 6.5 min / ℃. After carbonization, the material enters the deposition furnace for deposition treatment. Under nitrogen protection, the temperature is raised to 850℃, and benzene (pure benzene) is introduced at a rate of 40 g / min for pore adjustment. The addition time is 25 min. After the addition is completed, the material is kept at this temperature for 3.5 h and then cooled. The process involves detection and sieving (dust generated during sieving – G6 – is collected using a bag filter; defective products obtained from sieving are returned to the deposition furnace for re-deposition) to obtain the finished product, namely CMS carbon molecular sieve with an average particle size of 1.5 mm. VOCs and other pollutants generated during the carbonization and deposition process (G7) are collected through pipelines and then sent to the main incinerator for combustion, achieving a combustion completion rate of over 90%. The gas then enters the regenerative dust removal chamber, undergoes the first dust removal, and then enters the auxiliary combustion furnace for residual waste gas incineration. After being cooled by water cooling tower, the gas is discharged through a 15 m high exhaust stack to meet emission standards (G8).

[0032] Example 3 The method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials in this embodiment includes the following steps: 1) Weigh phenolic resin waste and phenolic resin virgin with a moisture content of 10%-15% according to a mass ratio of 1:3. Then, crush them separately using a pulverizer, generating a small amount of dust (G1). The crushed material is then dried once in a dryer, generating a small amount of dust at the end of the dryer (G2). The drying temperature is 180℃ and the time is 2 hours. After the first drying, the material is ball-milled into a fine powder, generating ball milling dust (G3). The fine powder is then dried a second time in a dryer, generating a small amount of dust at the end of the dryer (G4). The drying temperature is 175℃ and the time is 1.8 hours, resulting in resin powder with a moisture content of 7% and an average particle size of 20μm. 2) The resin powder, starch, chitosan, coal tar, asphalt and water are mixed and stirred in a mass ratio of 70:4:1:5:3:60. A small amount of dust will be generated during the mixing process (G5). The mixture is then fed into an automatic temperature-controlled kneader. After being kneaded evenly in the kneader, it is then extruded into shape by a twin-screw extruder to obtain the base material. A small amount of fugitive organic waste gas will be volatilized during the discharge process of the kneader (Gu1). 3) The base material enters the carbonization furnace cylinder for carbonization. In the first stage, the temperature is raised to 310℃ at a heating rate of 2.2 min / ℃. In the second stage, the temperature is raised to 660℃ at a heating rate of 5.5 min / ℃. Finally, in the third stage, the temperature is raised to 845℃ at a heating rate of 4 min / ℃. After carbonization, the material enters the deposition furnace for deposition treatment. Under nitrogen protection, the temperature is raised to 800℃, and benzene (pure benzene) is introduced at a rate of 35 g / min for pore adjustment. The addition time is 30 min, and the material is held at this temperature for 3 hours after addition. After cooling, the material is inspected. The process involves measurement and sieving (dust generated during sieving – G6 – is collected using a bag filter; defective products obtained from sieving are returned to the deposition furnace for re-deposition) to obtain the finished product, namely CMS carbon molecular sieve with an average particle size of 1.3 mm. Pollutants such as VOCs generated during carbonization and deposition (G7) are collected through pipelines and then burned in the main incinerator, achieving a combustion completion rate of over 90%. The waste gas then enters the regenerative dust removal chamber, undergoes the first dust removal, and then enters the auxiliary combustion furnace for residual waste gas incineration. After being cooled by water cooling tower, the waste gas is discharged through a 15m high exhaust stack to meet emission standards (G8).

[0033] Example 4 The method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials in this embodiment includes the following steps: 1) Weigh phenolic resin waste and phenolic resin virgin material with a moisture content of 10%-15% according to a mass ratio of 1:3. Then, crush them separately using a pulverizer, generating a small amount of dust (G1). The crushed material is then dried once in a dryer, generating a small amount of dust at the end of the dryer (G2). The drying temperature is 150℃ and the time is 2.5h. After the first drying, the material is ball-milled into a fine powder, generating ball milling dust (G3). The fine powder is then dried a second time in a dryer, generating a small amount of dust at the end of the dryer (G4). The drying temperature is 180℃ and the time is 1h, resulting in resin powder with a moisture content of 5% and an average particle size of 5μm. 2) The resin powder, porous nanotubes, starch, chitosan, coal tar, asphalt and water are mixed and stirred in a mass ratio of 70:1:4:1:5:3:60. A small amount of dust will be generated during the mixing process (G5). The mixture is then fed into an automatic temperature-controlled kneader. After being kneaded evenly in the kneader, it is then extruded into shape by a twin-screw extruder to obtain the base material. A small amount of fugitive organic waste gas will be volatilized during the discharge process of the kneader (Gu1). 3) The base material enters the cylinder of the carbonization furnace for carbonization. In the first stage, the temperature is raised to 300℃ at a heating rate of 2 min / ℃. In the second stage, the temperature is raised to 650℃ at a heating rate of 6 min / ℃. Finally, in the third stage, the temperature is raised to 840℃ at a heating rate of 3.5 min / ℃. After carbonization, the material enters the deposition furnace for deposition treatment. Under nitrogen protection, the temperature is raised to 750℃, and benzene (pure benzene) is introduced at a rate of 30 g / min for pore adjustment. The addition time is 35 min, and the material is kept at this temperature for 2.5 h after addition. After cooling... The process involves detection and sieving (dust generated during sieving – G6 – is collected using a bag filter; defective products obtained from sieving are returned to the deposition furnace for re-deposition) to obtain the finished product, namely CMS carbon molecular sieve with an average particle size of 1mm. VOCs and other pollutants generated during the carbonization and deposition process (G7) are collected through pipelines and then sent to the main incinerator for combustion, achieving a combustion completion rate of over 90%. The gas then enters the regenerative dust removal chamber, undergoes the first dust removal, and then enters the auxiliary combustion furnace for residual waste gas incineration. After being cooled by water cooling tower, the gas is discharged through a 15m high exhaust stack to meet emission standards (G8).

[0034] The method for preparing porous nanotubes in this embodiment is as follows: 1) Weigh 50g zinc nitrate hexahydrate, 0.75g calcium chloride, 200g ethanol, 50g polyvinylpyrrolidone, and 430g dimethylformamide and mix them. Control the stirring speed at 200rpm and stir for 2h to obtain the precursor solution. 2) The precursor solution was transferred to a glass syringe with a stainless steel needle and electrospinned at a voltage of 12kV. The distance between the needle and the collecting plate was 19cm. The obtained fibers were kept at 600℃ for 2h in a high-temperature annealing furnace, crushed, and passed through a 250-mesh sieve to obtain porous nanotubes.

[0035] Example 5 The method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials in this embodiment includes the following steps: 1) Weigh phenolic resin waste and phenolic resin virgin material with a moisture content of 10%-15% according to a mass ratio of 1:3. Then, crush them separately using a pulverizer, generating a small amount of dust (G1). The crushed material is then dried once in a dryer, generating a small amount of dust at the end of the dryer (G2). The drying temperature is 150℃ and the time is 2.5h. After the first drying, the material is ball-milled into a fine powder, generating ball milling dust (G3). The fine powder is then dried a second time in a dryer, generating a small amount of dust at the end of the dryer (G4). The drying temperature is 180℃ and the time is 1h, resulting in resin powder with a moisture content of 5% and an average particle size of 5μm. 2) The resin powder, porous nanotubes, starch, chitosan, coal tar, asphalt and water are mixed and stirred in a mass ratio of 70:1:4:1:5:3:60. A small amount of dust will be generated during the mixing process (G5). The mixture is then fed into an automatic temperature-controlled kneader. After being kneaded evenly in the kneader, it is extruded and shaped by a twin-screw extruder to obtain the base material. A small amount of fugitive organic waste gas will be volatilized during the discharge process of the kneader (Gu1). 3) The base material enters the cylinder of the carbonization furnace for carbonization. In the first stage, the temperature is raised to 300℃ at a heating rate of 2 min / ℃. In the second stage, the temperature is raised to 650℃ at a heating rate of 6 min / ℃. Finally, in the third stage, the temperature is raised to 840℃ at a heating rate of 3.5 min / ℃. After carbonization, the material enters the deposition furnace for deposition treatment. Under nitrogen protection, the temperature is raised to 750℃, and benzene (pure benzene) is introduced at a rate of 30 g / min for pore adjustment. The addition time is 35 min, and the material is kept at this temperature for 2.5 h after addition. After cooling... The process involves detection and sieving (dust generated during sieving – G6 – is collected using a bag filter; defective products obtained from sieving are returned to the deposition furnace for re-deposition) to obtain the finished product, namely CMS carbon molecular sieve with an average particle size of 1mm. VOCs and other pollutants generated during the carbonization and deposition process (G7) are collected through pipelines and then sent to the main incinerator for combustion, achieving a combustion completion rate of over 90%. The gas then enters the regenerative dust removal chamber, undergoes the first dust removal, and then enters the auxiliary combustion furnace for residual waste gas incineration. After being cooled by water cooling tower, the gas is discharged through a 15m high exhaust stack to meet emission standards (G8).

[0036] The method for preparing porous nanotubes in this embodiment is as follows: 1) Weigh 50g zinc nitrate hexahydrate, 0.75g calcium chloride, 200g ethanol, 40g polyvinylpyrrolidone, and 430g dimethylformamide and mix them. Control the stirring speed at 200rpm and stir for 2h to obtain the precursor solution. 2) The precursor solution was transferred to a glass syringe with a stainless steel needle and electrospinned. The voltage was 12.5kV and the distance between the needle and the collecting plate was 18cm. The obtained fibers were kept at 650℃ for 2h in a high-temperature annealing furnace, crushed, and passed through a 250-mesh sieve to obtain porous nanotubes.

[0037] Comparative Example 1 The method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials in this comparative example includes the following steps: 1) Weigh 1 kg of virgin phenolic resin and then pulverize it using a pulverizer, generating a small amount of dust (G1). The pulverized material is then dried once in a dryer, generating a small amount of dust (G2) at the end of the dryer. The drying temperature is 150℃ and the time is 2.5 h. After the first drying, the material is ball-milled into a fine powder, generating ball milling dust (G3) during the ball milling process. The fine powder is then dried a second time in a dryer, generating a small amount of dust (G4) at the end of the dryer. The drying temperature is 180℃ and the time is 1 h, resulting in resin powder with a moisture content of 5% and an average particle size of 5 μm. 2) Mix resin powder, starch, chitosan, coal tar, asphalt and water in a mass ratio of 70:4:1:5:3:60. A small amount of dust will be generated during the mixing process (G5). The mixture is then fed into an automatic temperature-controlled kneader. After being kneaded evenly in the kneader, it is extruded into shape by a twin-screw extruder to obtain the base material. A small amount of fugitive organic waste gas will be volatilized during the discharge process of the kneader (Gu1). 3) The base material enters the cylinder of the carbonization furnace for carbonization. In the first stage, the temperature is raised to 300℃ at a heating rate of 2 min / ℃. Then, in the second stage, the temperature is raised to 650℃ at a heating rate of 6 min / ℃. Finally, in the third stage, the temperature is raised to 840℃ at a heating rate of 3.5 min / ℃. After carbonization, the material enters the deposition furnace for deposition treatment. Under nitrogen protection, the temperature is raised to 750℃, and benzene (pure benzene) is introduced at a rate of 30 g / min for pore adjustment. The addition time is 35 min. After the addition is completed... After being kept at a constant temperature for 2.5 hours, cooled, tested, and sieved (dust generated during the sieving process - G6 - is collected by a bag filter), the finished product, namely CMS carbon molecular sieve with an average particle size of 1 mm, is obtained. The VOCs and other pollutants generated during the carbonization and deposition process (G7) are collected through pipelines and sent to the main incinerator for combustion, with a combustion completion rate of over 90%. Then, the gas enters the regenerative dust removal chamber, undergoes the first dust removal, and then enters the auxiliary combustion furnace for residual waste gas incineration. After being cooled by water cooling tower, the gas is discharged in compliance with standards through a 15 m high exhaust stack (G8).

[0038] Performance testing 1. Compressive strength: The compressive strength of CMS carbon molecular sieve was tested using a particle strength tester. The test results are shown in Table 1.

[0039] 2. Nitrogen production performance: The nitrogen production performance of CMS carbon molecular sieve was tested according to the standard HG / T 4364-2012. The adsorption pressure was 0.8 MPa and the adsorption period was 120 s. The test results are shown in Table 1.

[0040] Table 1 Performance test results Analysis of Examples 1-5 and Comparative Example 1, along with Table 1, shows that using phenolic resin waste and virgin phenolic resin in the preparation of CMS carbon molecular sieves effectively improves the nitrogen production and compressive strength of the CMS carbon molecular sieves. Adding porous nanotubes during the preparation of CMS carbon molecular sieves further enhances their compressive strength, thereby improving the nitrogen production performance of CMS carbon.

[0041] Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials, characterized in that: Includes the following steps: 1) Phenolic resin is pulverized, dried once, ground, and then dried a second time to obtain resin powder; 2) Mix resin powder, pore-forming agent, and additives, extrude, carbonize, and deposit to obtain CMS carbon molecular sieve.

2. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 1, characterized in that: In step 1), the phenolic resin includes waste phenolic resin and virgin phenolic resin.

3. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 1, characterized in that: In step 1), the drying temperature is 150-200℃ and the time is 1.5-2.5h. And / or, the secondary drying temperature is 160-180℃, and the time is 1-2 hours.

4. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 1, characterized in that: In step 1), the particle size of the resin powder is 5-30 μm.

5. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming materials according to claim 1, characterized in that: In step 2), the pore-forming agent includes starch and chitosan; And / or, the additives include coal tar, bitumen, and water.

6. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 1, characterized in that: In step 2), carbonization includes a first stage, a second stage, and a third stage; The first stage involves raising the temperature to 300-320℃ at a heating rate of 2-2.5 min / ℃. The second stage involves raising the temperature to 650-670℃ at a heating rate of 4-6 min / ℃. The third stage involves raising the temperature to 840-850℃ at a heating rate of 3.5-6.5 min / ℃.

7. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 1, characterized in that: In step 2), the specific deposition process is as follows: adjust the temperature to 750-850℃, introduce benzene at a rate of 30-40g / min to adjust the pore size, add the benzene for 25-35min, and keep warm for 2.5-3.5h after the addition is completed.

8. A method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 1 or 5, characterized in that: The additives also include porous nanotubes; The method for preparing the porous nanotubes includes the following steps: S1: Take water-soluble zinc salt, water-soluble calcium salt, polyvinylpyrrolidone, and solvent, mix them evenly to obtain the precursor solution; S2: Electrospinning the precursor solution to obtain fibers, which are then calcined, pulverized, and sieved to obtain porous nanotubes.

9. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 8, characterized in that: In step S1, the solvent includes ethanol and N,N-dimethylformamide.

10. The method for preparing CMS carbon molecular sieves based on phenolic resin foaming material according to claim 8, characterized in that: In step S2, the electrospinning process parameters are: voltage 12-12.5kV, receiving distance 18-19cm.

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