Method for preparing CMS carbon molecular sieve from flower soil recycling waste and application

Abstract

The application belongs to the technical field of carbon molecular sieve and specifically provides a method for preparing CMS carbon molecular sieve from waste flower clay and application thereof. The method comprises the following steps: 1) crushing, grinding and drying phenolic resin flower clay to obtain a precursor; 2) uniformly mixing raw materials including the precursor, starch, coal tar, pitch and water, and extruding to obtain carbonized material; and 3) performing carbonization and deposition treatment on the carbonized material. The molecular sieve prepared by the method has the advantages of high strength, good selectivity and high separation efficiency.

Description

Technical Field

[0001] This application belongs to the field of carbon molecular sieve technology, and in particular relates to a method and application for preparing CMS carbon molecular sieves from recycled flower mud waste. Background Technology

[0002] Carbon molecular sieves (CMS) are a special type of activated carbon with a bilevel pore structure and uniform micropore distribution, exhibiting high gas separation selectivity. They are prepared from high-carbon-content materials through high-temperature pyrolysis. Numerous carbon precursors can be used to prepare CMS, including polymer precursors, bituminous precursors, and biomass precursors. Polymer precursors are widely available, such as resins and polyurethanes. By selecting appropriate chemical reagents and carbonization processes, the pore structure, surface chemical composition, and catalytic activity of porous carbon can be improved.

[0003] Compared to materials like MOFs and zeolite molecular sieves, which face challenges in stability, high price, and particle formation, carbon molecular sieves possess advantages such as excellent structural and chemical stability, lower preparation costs, and wider availability. Using polymer precursors as carbon sources offers advantages such as simple structure and low impurity content. Commonly used polymers are thermosetting phenolic resins or phenolic resin foam materials prepared through phenolic resin foaming processes. This type of phenolic resin foam material is called "phenolic foam," and the use of phenolic foam as a raw material for preparing carbon molecular sieves is increasingly favored by technicians.

[0004] For example, patent application publication number CN120288743A discloses a phenolic resin modified carbon molecular sieve, including the following steps: a) In-situ polymerization: phenolic resin polymerization mother liquor and carbon molecular sieve are mixed, and after static adsorption, the adsorbed carbon molecular sieve is heated to carry out a polymerization reaction to obtain a polymerization product; the phenolic resin polymerization mother liquor includes phenolic substances, aldehyde substances and solvents; b) Carbonization modification: the polymerization product is calcined under a protective atmosphere to obtain a phenolic resin modified carbon molecular sieve, which has selective adsorption properties and can be applied in the N2 / CH4 system, selectively adsorbing N2 with a high separation ratio and good stability.

[0005] For example, patent application CN111087561A discloses a production process for granular phenolic resin. The process involves the polymerization of phenol and formaldehyde under the catalysis of an acidic or alkaline catalyst. Before the reaction, an emulsifier is added to bring the reaction solution to an appropriate viscosity and suspension dispersion at a specific reaction temperature. The polymerization reaction is carried out under thorough stirring to generate granular phenolic resin. The phenolic resin is then cured by extending the reaction time or adding a curing agent. The phenolic resin is then washed, filtered, and dried to obtain uniform, cured granular phenolic resin with a particle size of less than 10 μm, which is used in the production of carbon molecular sieves to improve the adsorption performance of carbon molecular sieves.

[0006] The aforementioned documents continuously improve the process for preparing carbon molecular sieves and enhance their performance. However, with the continuous advancement of pressure swing adsorption technology, exploring more advanced porous carbon material preparation technologies to produce carbon molecular sieves with excellent selectivity is of great demand and practical significance. Summary of the Invention

[0007] To address the aforementioned issues and further improve the performance of carbon molecular sieves in pressure swing adsorption technology, this application provides a method and application for preparing CMS carbon molecular sieves from recycled flower mud waste.

[0008] This application first provides a method for preparing CMS carbon molecular sieves from recycled floral foam waste, including the following steps:

[0009] 1) Phenolic resin floral foam is crushed, ground, and dried to obtain precursor material;

[0010] 2) Mix raw materials including precursors, starch, tar, asphalt and water evenly, and extrude them to obtain carbonized material;

[0011] 3) The carbonized material is carbonized and deposited to obtain the final product.

[0012] Furthermore, in step 1), the particle size of the precursor material is 5-30 μm.

[0013] Furthermore, in step 1), the moisture content of the precursor material is 5-8%.

[0014] Furthermore, in step 1), the drying temperature is 150-200℃.

[0015] Furthermore, in step 2), an interface agent is added during the mixing process. The interface agent is prepared using the following steps:

[0016] S1: Mix glycerol, choline chloride, and water thoroughly, then add N-(2-hydroxyethyl)acrylamide and stir to dissolve to obtain the pretreatment solution;

[0017] S2: The photoinitiator is added to the pre-solvent to carry out a photopolymerization reaction.

[0018] Furthermore, in step 3), carbonization includes a first stage, a second stage, and a third stage. The first stage is performed at a temperature of 300°C, the second stage is performed at a temperature of 300-650°C, and the third stage is performed at a temperature of 650-850°C.

[0019] Furthermore, in step 3), the carbonization treatment time is 4-5 hours.

[0020] Furthermore, in step 3), the deposition is carried out by heating to 800-850°C under nitrogen protection and introducing pure benzene for deposition treatment.

[0021] Furthermore, in step 3), the deposition treatment time is 2.5-3.5 hours.

[0022] This application also provides an application of CMS carbon molecular sieve prepared from recycled flower mud waste, wherein the CMS carbon molecular sieve prepared by the above method is used for nitrogen separation.

[0023] Compared with the prior art, this application has the following beneficial effects:

[0024] 1. This application uses phenolic foam as a precursor material, which has a micro-open-pore structure. It is combined with starch, tar oil and asphalt, etc., and through a three-stage carbonization process, to form a denser and more crystalline microstructure, making the pore size distribution of the molecular sieve more uniform and the pore structure richer, resulting in higher gas separation efficiency and stability.

[0025] 2. This application adds an interface agent to the raw materials to enhance the strength of the carbon molecular sieve skeleton structure by utilizing the adhesion of multiple hydrogen bonds. It also reduces the clogging of the pores during carbonization and deposition processes, adjusts the pore structure inside the molecular sieve, increases the mass transfer ratio of nitrogen or methane molecules in the pores, and has high strength and wear resistance. Attached Figure Description

[0026] Figure 1 This is a production flow diagram of the CMS carbon molecular sieve in this application. Detailed Implementation

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] In this application, "above" or "below" includes the number itself. For example, "below 1" includes 1.

[0036] In this application, room temperature refers to 0~40℃, including but not limited to 10~40℃, or further to 20~30℃.

[0037] This application, based on extensive experimental research, provides a method for preparing CMS carbon molecular sieves from recycled floral foam, comprising the following steps:

[0038] 1) Phenolic resin floral foam is crushed, ground, and dried to obtain precursor material;

[0039] 2) Mix raw materials including precursors, starch, tar, asphalt and water evenly, and extrude them to obtain carbonized material;

[0040] 3) The carbonized material is carbonized and deposited to obtain the final product.

[0041] Furthermore, in step 1), the particle size of the precursor material is 5-30 μm.

[0042] In some specific embodiments, in step 1), the particle size of the precursor material can be 5-10μm, 10-15μm, 15-20μm, 20-25μm, or 25-30μm.

[0043] Furthermore, in step 1), the moisture content of the precursor material is 5-8%.

[0044] In some specific embodiments, in step 1), the moisture content of the precursor material can be 5-5.5%, 5.5-6%, 6-6.5%, 6.5-7%, 7-7.5%, or 7.5-8%.

[0045] Furthermore, in step 1), the drying temperature is 150-200℃.

[0046] In some specific embodiments, the drying temperature in step 1) can be 150-160℃, 160-170℃, 170-180℃, 180-190℃, or 190-200℃.

[0047] Furthermore, in step 2), an interface agent is added during the mixing process. The interface agent is prepared using the following steps:

[0048] S1: Mix glycerol, choline chloride, and water thoroughly, then add N-(2-hydroxyethyl)acrylamide and stir to dissolve to obtain the pretreatment solution;

[0049] S2: The photoinitiator is added to the pre-solvent to carry out a photopolymerization reaction.

[0050] Furthermore, in step 3), carbonization includes a first stage, a second stage, and a third stage. The first stage is performed at a temperature of 300°C, the second stage is performed at a temperature of 300-650°C, and the third stage is performed at a temperature of 650-850°C.

[0051] Furthermore, in step 3), the carbonization treatment time is 4-5 hours.

[0052] In some specific embodiments, the carbonization time in step 3) can be 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h, or 5h. More preferably, a carbonization time of 4.5h in step 3) can achieve better technical results.

[0053] Furthermore, in step 3), the deposition is carried out by heating to 800-850°C under nitrogen protection and introducing pure benzene for deposition treatment.

[0054] In some specific embodiments, in step 3), the deposition can be carried out by heating to 800°C, 810°C, 820°C, 830°C, 840°C, or 850°C under nitrogen protection. More preferably, in step 3), heating to 800°C under nitrogen protection and introducing pure benzene for deposition treatment can achieve better experimental results.

[0055] Furthermore, in step 3), the deposition treatment time is 2.5-3.5 hours.

[0056] In some specific embodiments, the deposition treatment time in step 3) can be 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3.0h, 3.1h, 3.2h, 3.3h, 3.4h, or 3.5h. More preferably, a deposition treatment time of 3h can achieve better experimental results.

[0057] This application also provides an application of CMS carbon molecular sieve prepared from recycled flower mud waste, wherein the CMS carbon molecular sieve prepared by the above method is used for nitrogen separation.

[0058] The following is through Figure 1 The embodiments and examples further illustrate this application, but do not limit the scope of this application.

[0059] 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.

[0060] Example 1

[0061] The method for preparing CMS carbon molecular sieves from recycled floral foam in this embodiment includes the following steps:

[0062] 1) Phenolic resin floral foam is pulverized using a pulverizer, generating a small amount of crushing dust (G1) during this process. The pulverized material is then dried in a dryer at 150℃. The material enters the drum through a feeding device, while the high-temperature flue gas from the incinerator circulates repeatedly within the pipes on the outer layer of the drum. Driven by the lifting plates, the material is continuously lifted and scattered in a spiral motion to achieve heat exchange, thereby continuously evaporating moisture and drying the material. The drying time is approximately 1.5 hours, during which a small amount of dust (G2) is generated. The dried material is then ball-milled into a micro-powdered precursor, with the particle size of the precursor controlled. The material has a particle size of 5-30 μm and is transported to a storage tank via pipeline for later use. During the grinding process, ball mill dust (G3) is generated. After grinding into powder, the material undergoes a second drying process, lasting 1 hour. A small amount of dust (G4) is generated at the end of the dryer. The final moisture content of the precursor is controlled at 5-8%. Small amounts of free formaldehyde, phenols, and water vapor generated during the two drying processes are collected via pipeline condensation and sent to the extrusion molding section for reuse. In this embodiment, the precursor material has an ash content of 2.68%, a volatile matter content of 40.32%, a moisture content of 5.82%, and a fixed carbon content of 51.18%.

[0063] 2) Mix 3kg of precursor material, 100g of starch, 50g of tar oil, 50g of asphalt and an appropriate amount of water. A small amount of dust (G5) will be generated during the mixing process. After the mixture is evenly mixed, it is fed into an automatic temperature-controlled kneader. After being kneaded evenly by the kneader, it is extruded by a twin-screw extruder to obtain carbonized material. The purpose of kneading is to make the carbonized material have a certain viscosity and to prevent the volatilization of organic waste gas. The kneader is covered and sealed. A small amount of organic waste gas will volatilize during the operation of the kneader (Gu1).

[0064] 3) Carbonized materials are fed into the cylinder of the carbonization furnace in batches. The cylinder rotates and is continuously heated by resistance wires. During the pyrolysis process, various functional groups, bridging bonds, free radicals, and aromatic rings undergo decomposition and polymerization reactions. The thermally unstable components are released as volatiles. The purpose is to develop the pores of the carbonized product and expand or shrink the pore size. The carbonization process is divided into three stages: the first stage is 0~300℃, and the exhaust gas is mainly water vapor, containing a small amount of low-carbon organic matter and some volatile organic matter; the second stage is 300~650℃, and the exhaust gas is mainly high-carbon organic matter. The exhaust gas can spontaneously combust, and with the help of air, it can burn violently to produce high temperatures; the third stage is 650~850℃, and the exhaust gas is mainly H2 and CO from the decomposition of the material. It can spontaneously combust, and the carbonization time is about 4 hours.

[0065] After carbonization, the material enters a deposition furnace for deposition. Under nitrogen protection, the temperature is raised to 800℃, and pure benzene is introduced at a rate of 35 g / min to adjust the pore size. The addition time is 30 min. The introduced benzene rapidly decomposes into a C and H mixture at high temperature. C is deposited on the walls of the micropores of the material, thereby reducing the diameter of the product pores. H and C can form CH4 gas, which is emitted. A small amount of benzene vapor is present in the exhaust gas. The deposition time is approximately 2.5 h, at which point the product is obtained.

[0066] The first stage of the carbonization process mainly produces water vapor and VOCs in the exhaust gas. In the second and third stages, due to the higher temperatures, all VOCs are decomposed into H2, CO, methane, etc. The deposition process generates methane and a small amount of VOCs. The VOCs and other pollutants (G7) generated during the carbonization and deposition process are collected through pipelines and sent to the main incinerator for combustion, achieving a combustion rate of over 90%. The gas then enters a regenerative thermal precipitator for initial dust removal before being sent to an auxiliary combustion furnace for residual gas combustion. After cooling in a water-cooled tower, the gas is discharged through a 15m high exhaust stack to meet emission standards (G8). The cooling water is recycled and replenished periodically. The large amount of waste heat generated during combustion is delivered via hot air pipelines to provide indirect heating energy for the raw material drying system. The main incinerator uses #0 diesel oil as auxiliary fuel, and the auxiliary combustion furnace uses biomass pellets as auxiliary fuel. Through secondary combustion, the exhaust gas combustion rate reaches over 98%. Because the equipment cannot be perfectly sealed during the carbonization and deposition process, a small amount of fugitive volatile gas (Gu2) is generated. A gas collection hood is installed above the carbonization furnace and the deposition furnace. The unorganized volatile gases are collected by the induced draft fan, absorbed by the workshop water spray device, and then discharged into the atmosphere from the 15-meter-high exhaust stack.

[0067] After sedimentation, the discharged material undergoes inspection and sieving, with the particle size controlled at approximately 1-1.5 mm. Qualified products are stored in the warehouse, while substandard products are returned for repeated sedimentation. According to company experience, the pass rate for the first sedimentation is generally 85%, and the second sedimentation achieves near-complete pass rate. Dust (G6) generated during the sieving process is collected using a bag filter.

[0068] Example 2

[0069] The method for preparing CMS carbon molecular sieves from recycled floral foam in this embodiment includes the following steps:

[0070] 1) Phenolic resin floral foam is pulverized using a pulverizer, generating a small amount of crushing dust (G1) during this process. The pulverized material is then dried in a dryer at 200℃. The material enters the drum through a feeding device, while the high-temperature flue gas from the incinerator circulates repeatedly within the pipes on the outer layer of the drum. Driven by the lifting plates, the material is continuously lifted and scattered in a spiral motion to achieve heat exchange, thereby continuously evaporating moisture and drying the material. The drying time is approximately 1.5 hours, during which a small amount of dust (G2) is generated. The dried material is then ball-milled into a micro-powdered precursor, with the particle size of the precursor controlled. The material has a particle size of 5-30 μm and is transported to a storage tank via pipeline for later use. During the grinding process, ball mill dust (G3) is generated. After grinding into powder, the material undergoes a second drying process, lasting 1 hour. A small amount of dust (G4) is generated at the end of the dryer. The final moisture content of the precursor is controlled at 5-8%. Small amounts of free formaldehyde, phenols, and water vapor generated during the two drying processes are collected via pipeline condensation and sent to the extrusion molding section for reuse. In this embodiment, the precursor material has an ash content of 2.68%, a volatile matter content of 40.32%, a moisture content of 5.82%, and a fixed carbon content of 51.18%.

[0071] 2) Mix 3kg of precursor material, 100g of starch, 50g of tar oil, 50g of asphalt and an appropriate amount of water. A small amount of dust (G5) will be generated during the mixing process. After the mixture is evenly mixed, it is fed into an automatic temperature-controlled kneader. After being kneaded evenly by the kneader, it is extruded by a twin-screw extruder to obtain carbonized material. The purpose of kneading is to make the carbonized material have a certain viscosity and to prevent the volatilization of organic waste gas. The kneader is covered and sealed. A small amount of organic waste gas will volatilize during the operation of the kneader (Gu1).

[0072] 3) Carbonized materials are fed into the cylinder of the carbonization furnace in batches. The cylinder rotates and is continuously heated by resistance wires. During the pyrolysis process, various functional groups, bridging bonds, free radicals, and aromatic rings undergo decomposition and polymerization reactions. The resulting thermally unstable components are released as volatiles. The purpose is to develop the pores of the carbonized product, expanding or shrinking the pore size. The carbonization process is divided into three stages: the first stage is 0~300℃, and the exhaust gas is mainly water vapor, containing a small amount of low-carbon organic matter and some volatile organic matter; the second stage is 300~650℃, and the exhaust gas is mainly high-carbon organic matter. The exhaust gas can spontaneously combust, and with the help of air, it can burn violently, generating high temperatures; the third stage is 650~850℃, and the exhaust gas is mainly H2 and CO from the decomposition of the material. It can spontaneously combust, and the carbonization time is about 5 hours.

[0073] After carbonization, the material is transferred to a deposition furnace for deposition. Under nitrogen protection, the temperature is raised to 800℃, and pure benzene is introduced at a rate of 35 g / min to adjust the pore size. The addition time is 30 min. The introduced benzene rapidly decomposes into a C and H mixture at high temperature. C is deposited on the walls of the micropores of the material, thereby reducing the diameter of the product pores. H and C can form CH4 gas, which is emitted. A small amount of benzene vapor is present in the exhaust gas. The deposition time is approximately 3.5 h, at which point the product is obtained.

[0074] The first stage of the carbonization process mainly produces water vapor and VOCs in the exhaust gas. In the second and third stages, due to the higher temperatures, all VOCs are decomposed into H2, CO, methane, etc. The deposition process generates methane and a small amount of VOCs. The VOCs and other pollutants (G7) generated during the carbonization and deposition process are collected through pipelines and sent to the main incinerator for combustion, achieving a combustion rate of over 90%. The gas then enters a regenerative thermal precipitator for initial dust removal before being sent to an auxiliary combustion furnace for residual gas combustion. After cooling in a water-cooled tower, the gas is discharged through a 15m high exhaust stack to meet emission standards (G8). The cooling water is recycled and replenished periodically. The large amount of waste heat generated during combustion is delivered via hot air pipelines to provide indirect heating energy for the raw material drying system. The main incinerator uses #0 diesel oil as auxiliary fuel, and the auxiliary combustion furnace uses biomass pellets as auxiliary fuel. Through secondary combustion, the exhaust gas combustion rate reaches over 98%. Because the equipment cannot be perfectly sealed during the carbonization and deposition process, a small amount of fugitive volatile gas (Gu2) is generated. A gas collection hood is installed above the carbonization furnace and the deposition furnace. The unorganized volatile gases are collected by the induced draft fan, absorbed by the workshop water spray device, and then discharged into the atmosphere from the 15-meter-high exhaust stack.

[0075] After sedimentation, the discharged material undergoes inspection and sieving, with the particle size controlled at approximately 1-1.5 mm. Qualified products are stored in the warehouse, while substandard products are returned for repeated sedimentation. According to company experience, the pass rate for the first sedimentation is generally 85%, and the second sedimentation achieves near-complete pass rate. Dust (G6) generated during the sieving process is collected using a bag filter.

[0076] Example 3

[0077] The method for preparing CMS carbon molecular sieves from recycled floral foam in this embodiment includes the following steps:

[0078] 1) Phenolic resin floral foam is pulverized using a pulverizer, generating a small amount of crushing dust (G1) during this process. The pulverized material is then dried in a dryer at 200℃. The material enters the drum through a feeding device, while the high-temperature flue gas from the incinerator circulates repeatedly within the pipes on the outer layer of the drum. Driven by the lifting plates, the material is continuously lifted and scattered in a spiral motion to achieve heat exchange, thereby continuously evaporating moisture and drying the material. The drying time is approximately 1.5 hours, during which a small amount of dust (G2) is generated. The dried material is then ball-milled into a micro-powdered precursor, with the particle size of the precursor controlled. The material has a particle size of 5-30 μm and is transported to a storage tank via pipeline for later use. During the grinding process, ball mill dust (G3) is generated. After grinding into powder, the material undergoes a second drying process, lasting 1 hour. A small amount of dust (G4) is generated at the end of the dryer. The final moisture content of the precursor is controlled at 5-8%. Small amounts of free formaldehyde, phenols, and water vapor generated during the two drying processes are collected via pipeline condensation and sent to the extrusion molding section for reuse. In this embodiment, the precursor material has an ash content of 2.68%, a volatile matter content of 40.32%, a moisture content of 5.82%, and a fixed carbon content of 51.18%.

[0079] 2) Mix 3kg of precursor material, 100g of starch, 50g of tar oil, 50g of asphalt, 50g of interface agent and appropriate amount of water. A small amount of dust will be generated during the mixing process (G5). After the mixture is evenly mixed, it enters an automatic temperature-controlled kneader. After being kneaded evenly by the kneader, it is then extruded by a twin-screw extruder to obtain carbonized material. The purpose of kneading is to make the carbonized material have a certain viscosity and to prevent the volatilization of organic waste gas. The kneader is covered and sealed. A small amount of organic waste gas will volatilize during the operation of the kneader (Gu1).

[0080] The interface agent in this embodiment is prepared using the following steps:

[0081] S1: Mix 50g glycerol, 20g choline chloride, and 10g water evenly, then add 5g N-(2-hydroxyethyl)acrylamide and 0.5g sodium chloride, stir to dissolve and obtain the pretreatment solution;

[0082] S2: Add photoinitiator (1.5% of the mass of N-(2-hydroxyethyl)acrylamide) to the pre-solvent, and carry out photopolymerization reaction at room temperature with ultraviolet light at a wavelength of 365nm and a power of 36w for 2 hours to obtain the product;

[0083] 3) Carbonized materials are fed into the cylinder of the carbonization furnace in batches. The cylinder rotates and is continuously heated by resistance wires. During the pyrolysis process, various functional groups, bridging bonds, free radicals, and aromatic rings undergo decomposition and polymerization reactions. The thermally unstable components are released as volatiles. The purpose is to develop the pores of the carbonized product and expand or shrink the pore size. The carbonization process is divided into three stages: the first stage is 0~300℃, and the exhaust gas is mainly water vapor, containing a small amount of low-carbon organic matter and some volatile organic matter; the second stage is 300~650℃, and the exhaust gas is mainly high-carbon organic matter. The exhaust gas can spontaneously combust, and with the help of air, it can burn violently to produce high temperatures; the third stage is 650~850℃, and the exhaust gas is mainly H2 and CO from the decomposition of the material. It can spontaneously combust, and the carbonization time is about 4 hours.

[0084] After carbonization, the material is transferred to a deposition furnace for deposition. Under nitrogen protection, the temperature is raised to 800℃, and pure benzene is introduced at a rate of 35 g / min to adjust the pore size. The addition time is 30 min. The introduced benzene rapidly decomposes into a C and H mixture at high temperature. C is deposited on the walls of the micropores of the material, thereby reducing the diameter of the fine pores in the product. H and C can form CH4 gas, which is emitted. A small amount of benzene vapor is present in the exhaust gas. The deposition time is about 3 hours, and the product is obtained.

[0085] The first stage of the carbonization process mainly produces water vapor and VOCs in the exhaust gas. In the second and third stages, due to the higher temperatures, all VOCs are decomposed into H2, CO, methane, etc. The deposition process generates methane and a small amount of VOCs. The VOCs and other pollutants (G7) generated during the carbonization and deposition process are collected through pipelines and sent to the main incinerator for combustion, achieving a combustion rate of over 90%. The gas then enters a regenerative thermal precipitator for initial dust removal before being sent to an auxiliary combustion furnace for residual gas combustion. After cooling in a water-cooled tower, the gas is discharged through a 15m high exhaust stack to meet emission standards (G8). The cooling water is recycled and replenished periodically. The large amount of waste heat generated during combustion is delivered via hot air pipelines to provide indirect heating energy for the raw material drying system. The main incinerator uses #0 diesel oil as auxiliary fuel, and the auxiliary combustion furnace uses biomass pellets as auxiliary fuel. Through secondary combustion, the exhaust gas combustion rate reaches over 98%. Because the equipment cannot be perfectly sealed during the carbonization and deposition process, a small amount of fugitive volatile gas (Gu2) is generated. A gas collection hood is installed above the carbonization furnace and the deposition furnace. The unorganized volatile gases are collected by the induced draft fan, absorbed by the workshop water spray device, and then discharged into the atmosphere from the 15-meter-high exhaust stack.

[0086] After sedimentation, the discharged material undergoes inspection and sieving, with the particle size controlled at approximately 1-1.5 mm. Qualified products are stored in the warehouse, while substandard products are returned for repeated sedimentation. According to company experience, the pass rate for the first sedimentation is generally 85%, and the second sedimentation achieves near-complete pass rate. Dust (G6) generated during the sieving process is collected using a bag filter.

[0087] Performance testing

[0088] The product performance was tested according to the HG / T 4364-2012 standard, and the test results are shown in Table 1.

[0089]

[0090] 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 from recycled floral foam waste, characterized in that: Includes the following steps: 1) Phenolic resin floral foam is crushed, ground, and dried to obtain precursor material; 2) The raw materials, including precursor, starch, tar, asphalt, interface agent and water, are mixed evenly and extruded to obtain carbonized material; the interface agent is prepared by the following steps: S1: Glycerol, choline chloride and water are mixed evenly, then N-(2-hydroxyethyl)acrylamide and sodium chloride are added and stirred to dissolve to obtain a pretreatment solution; S2: A photoinitiator is added to the pretreatment solution to carry out a photopolymerization reaction to obtain the final product; 3) The carbonized material is carbonized and deposited to obtain the product; the carbonization includes a first stage, a second stage and a third stage, the first stage is processed at a temperature of 300℃, the second stage is processed at a temperature of 300-650℃, and the third stage is processed at a temperature of 650-850℃.

2. The method for preparing CMS carbon molecular sieves from recycled floral foam according to claim 1, characterized in that: In step 1), the particle size of the precursor material is 5-30 μm.

3. The method for preparing CMS carbon molecular sieves from recycled floral foam according to claim 1, characterized in that: In step 1), the moisture content of the precursor material is 5-8%.

4. The method for preparing CMS carbon molecular sieves from recycled floral foam according to claim 1, characterized in that: In step 1), the drying temperature is 150-200℃.

5. The method for preparing CMS carbon molecular sieves from recycled floral foam according to claim 1, characterized in that: In step 3), the carbonization treatment time is 4-5 hours.

6. The method for preparing CMS carbon molecular sieves from recycled floral foam according to claim 1, characterized in that: In step 3), the deposition process involves heating the gas to 800-850°C under nitrogen protection and then introducing pure benzene for deposition treatment.

7. The method for preparing CMS carbon molecular sieves from recycled floral foam according to claim 1, characterized in that: In step 3), the deposition treatment time is 2.5-3.5 hours.

8. An application of CMS carbon molecular sieve prepared from recycled floral foam waste, characterized in that: The CMS carbon molecular sieve prepared by the method as described in any one of claims 1-7 can be used in the field of gas separation.

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