Method for preparing CMS carbon molecular sieve from flower mud recovery waste and application of CMS carbon molecular sieve

Abstract

The invention belongs to the technical field of carbon molecular sieves, and particularly provides a method for preparing a CMS carbon molecular sieve from flower mud recovery waste and application. Comprising 1) taking phenolic resin flower mud, crushing, grinding and drying the phenolic resin flower mud to prepare a precursor material, 2) uniformly mixing the precursor material, starch, coking coal oil, asphalt and water and carrying out extrusion molding to prepare a carbonized material, and 3) taking the carbonized material and carrying out carbonization and deposition treatment.The prepared molecular sieve has the advantages of high strength, good selectivity and high separation efficiency.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of carbon molecular sieve, and particularly relates to a method for preparing CMS carbon molecular sieve from flower mud waste and application thereof. BACKGROUND

[0002] Carbon molecular sieve (CMS) is a special activated carbon with a dual-level pore structure and uniform micropore distribution, and has high gas separation selectivity. It is prepared by high-temperature pyrolysis of a material with a high carbon content. The carbon precursors capable of preparing CMS are various, including polymer precursors, pitch precursors, and biomass precursors. Polymer precursors are widely available, such as resins and polyurethane, and by selecting appropriate chemical reagents and carbonization processes, the pore structure, surface chemical composition, and catalytic properties of the porous carbon can be improved.

[0003] Compared with MOFs, zeolite molecular sieves and other materials, carbon molecular sieve has excellent structural stability and chemical stability, low preparation cost, and wide sources. Using polymer precursors as carbon sources has the advantages of simple structure and low impurity content. The commonly used polymer is thermosetting phenolic resin or phenolic resin foam prepared by a phenolic resin foaming process. This phenolic resin foam is called “phenolic flower mud”. Using phenolic flower mud as raw material to prepare carbon molecular sieve is increasingly favored by technicians.

[0004] A phenolic resin modified carbon molecular sieve is disclosed in a patent document with the application publication number CN120288743A, which comprises the following steps: a, in-situ polymerization: mixing a phenolic resin polymerization mother liquor and a carbon molecular sieve, and after adsorption, the adsorbed carbon molecular sieve is heated for polymerization reaction to obtain a polymerization product; the phenolic resin polymerization mother liquor comprises a phenolic substance, an aldehyde substance and a solvent; b, carbonization modification: the polymerization product is calcined in a protective atmosphere to obtain a phenolic resin modified carbon molecular sieve, which has selective adsorption and can be applied in an N2 / CH4 system to selectively adsorb N2, has a high separation ratio and good stability.

[0005] A production process of powder and particle phenolic resin is disclosed in a patent document with the application publication number CN111087561A, which is a polymerization reaction of phenol and formaldehyde under the catalysis of an acidic catalyst or an alkaline catalyst. Before the reaction, an emulsifier is added to make the reaction solution have appropriate viscosity and suspension dispersion force at a specific reaction temperature, and the polymerization reaction is carried out under sufficient stirring to generate powder and particle phenolic resin. The generated phenolic resin is solidified by extending the reaction time or adding a curing agent, and then washed, filtered and dried to obtain uniform solidified powder and particle phenolic resin with a particle size of less than 10 um for the production of carbon molecular sieve, thereby improving the adsorption performance of the carbon molecular sieve.

[0006] The above documents continuously improve the process of preparing carbon molecular sieve and continuously improve the performance of molecular sieve. However, with the continuous progress of pressure swing adsorption technology, there is an important demand and practical significance to explore more advanced porous carbon material preparation technology to prepare carbon molecular sieve with excellent selectivity. SUMMARY

[0007] In view of the above problems, in order to further improve the performance of carbon molecular sieve in pressure swing adsorption technology, the application provides a method for preparing CMS carbon molecular sieve from flower mud recycling waste and application.

[0008] The application first provides a method for preparing CMS carbon molecular sieve from flower mud recycling waste, comprising the following steps: 1) crushing, grinding and drying phenolic resin flower mud to obtain a precursor; 2) uniformly mixing raw materials including the precursor, starch, coal tar, pitch and water, and extruding to obtain carbonized material; 3) taking the carbonized material for carbonization and deposition treatment.

[0009] Further, in the step 1), the particle size of the precursor is 5-30 μm.

[0010] Further, in the step 1), the water content of the precursor is 5-8%.

[0011] Further, in the step 1), the drying temperature is 150-200°C.

[0012] Further, in the step 2), an interfacial agent is also added when uniformly mixing, and the interfacial agent is prepared by the following steps: S1: uniformly mixing glycerol, choline chloride and water, then adding N-(2-hydroxyethyl) acrylamide, and stirring and dissolving to obtain a pre-solution; S2: adding a photoinitiator to the pre-solution to perform photopolymerization reaction to obtain.

[0013] Further, in the step 3), the carbonization includes a first stage, a second stage and a third stage, the first stage is treated at a temperature of 300°C, the second stage is treated at a temperature of 300-650°C, and the third stage is treated at a temperature of 650-850°C.

[0014] Further, in the step 3), the carbonization treatment time is 4-5h.

[0015] Further, in the step 3), the deposition is carried out under nitrogen protection, the temperature is raised to 800-850°C, and pure benzene is introduced for deposition treatment.

[0016] Further, in the step 3), the deposition treatment time is 2.5-3.5h.

[0017] The application also provides a use of a flower mud waste for preparing a CMS carbon molecular sieve, and the CMS carbon molecular sieve prepared by the preparation method is used for nitrogen separation.

[0018] Compared with the prior art, the application has the following beneficial effects: 1. The phenolic foam is used as a precursor in the application, has a small open pore structure, and is combined with starch, coal tar, pitch and the like, and is processed through a three-stage carbonization process, so that a more dense and crystalline microstructure is formed, the pore size distribution of the molecular sieve is more uniform, the pore structure is more abundant, and the gas separation efficiency and stability are higher.

[0019] 2. The interface agent is added to the raw material in the application, the strength of the skeleton structure of the carbon molecular sieve is improved by using the multiple hydrogen bond adhesion, the plugging of the pore is reduced during the carbonization and deposition treatment, the pore structure inside the molecular sieve is adjusted, the mass transfer separation ratio of the nitrogen or methane molecules in the pore is increased, and the strength and wear resistance are high. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is a production flowchart of the CMS carbon molecular sieve of the application. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be described clearly and completely below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the scope of protection of the application.

[0022] 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 the application belongs. The terminology used in the specification of the application herein is only for the purpose of describing specific embodiments and is not intended to limit the application. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0023] In the case of using "including", "having", and "containing" described herein, it is intended to cover non-exclusive inclusion, unless an explicit limiting term such as "only", "consisting of", etc. is used, another component can also be added.

[0024] The words "preferably," "more preferably," "most preferably," and the like, in the specification, mean that in certain situations, one or more preferred embodiments of the application can provide certain benefits, however, other embodiments can also be preferred for the same reasons or for other reasons. Furthermore, the description herein of one or more preferred embodiments, does not imply that a different embodiment is not also a preferred embodiment. That is, the use of "preferably," "more preferably," "most preferably," and the like, herein is merely to describe a particularly advantageous embodiment or example, and is not to be construed as limiting the scope of the application.

[0025] In the specification, "further," "furthermore," "in addition," and the like, are used to describe additional features, and are not used to limit the scope of the present application.

[0026] In the specification, "at least one" means one or more, i.e. one, two, three, etc. The meaning of "a," "an," and "the" is taken to be the same as "at least one" unless otherwise indicated. In the specification, "plurality" means at least two, i.e. two, three, four, etc. The meaning of "multiple" is at least two, e.g. two, three, etc. The meaning of "a plurality of" is at least two, e.g. two, three, etc., unless otherwise indicated.

[0027] When a range of values is disclosed, unless otherwise expressly stated, the end points of the range are included in the range, and each intervening value by the minimum and maximum value of the range is also included in the range. Further, when a range of values is provided, it is understood that each intervening value, to the minimum and maximum value of the range, is also contemplated, unless the context clearly indicates otherwise. Likewise, any reports provided herein as supporting the results of a suggested range of values should be considered to support the full range of values unless the context clearly indicates otherwise.

[0028] If not specifically stated, all steps of the application can be performed in any order. For example, the method comprises steps (a) and (b) means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method can further comprise step (c) means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc. Unless otherwise indicated, a singular form of a term can include a plural form of that term, and not understood as having a quantity of one.

[0029] In the specification, "above" or "below" includes the number itself. For example, 1 or less, includes 1.

[0030] In the present application, room temperature refers to 0-40℃, including but not limited to 10-40℃, or further 20-30℃.

[0031] The present application is based on a large number of experimental researches, and provides a method for preparing CMS carbon molecular sieve from flower mud waste, comprising the following steps: 1) crushing, grinding and drying phenolic resin flower mud to obtain a precursor; 2) uniformly mixing raw materials including the precursor, starch, coal tar, pitch and water, and extruding to obtain carbonized material; 3) taking the carbonized material to perform carbonization and deposition treatment.

[0032] Further, in the step 1), the particle size of the precursor is 5-30μm.

[0033] In some embodiments, in the step 1), the particle size of the precursor can be 5-10μm, 10-15μm, 15-20μm, 20-25μm, 25-30μm.

[0034] Further, in the step 1), the water content of the precursor is 5-8%.

[0035] In some embodiments, in the step 1), the water content of the precursor can be 5-5.5%, 5.5-6%, 6-6.5%, 6.5-7%, 7-7.5%, 7.5-8%.

[0036] Further, in the step 1), the drying temperature is 150-200℃.

[0037] In some embodiments, in the step 1), the drying temperature can be 150-160℃, 160-170℃, 170-180℃, 180-190℃, 190-200℃.

[0038] Further, in the step 2), an interfacial agent is also added when uniformly mixing, and the interfacial agent is prepared by the following steps: S1: uniformly mixing glycerol, choline chloride and water, then adding N-(2-hydroxyethyl) acrylamide, and stirring and dissolving to obtain a pre-liquid; S2: adding a photoinitiator to the pre-liquid to perform photopolymerization reaction to obtain.

[0039] Further, in the step 3), the carbonization includes a first stage, a second stage and a third stage, the first stage is treated at a temperature of 300℃, the second stage is treated at a temperature of 300-650℃, and the third stage is treated at a temperature of 650-850℃.

[0040] Further, in the step 3), the carbonization treatment time is 4-5h.

[0041] In some embodiments, in the step 3), the carbonization treatment time can be 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h, 5h. More preferably, in the step 3), the carbonization treatment time of 4.5h can achieve better technical effects.

[0042] Further, in the step 3), the deposition is under nitrogen protection, and the temperature is raised to 800-850℃, and pure benzene is introduced for deposition treatment.

[0043] In some embodiments, in the step 3), the deposition can be under nitrogen protection, and the temperature is raised to 800℃, 810℃, 820℃, 830℃, 840℃, 850℃. More preferably, in the step 3), the temperature is raised to 800℃ under nitrogen protection, and pure benzene is introduced for deposition treatment, which can achieve better experimental effects.

[0044] Further, in the step 3), the deposition treatment time is 2.5-3.5h.

[0045] In some embodiments, in the step 3), the deposition treatment time can be 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3.0h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h. More preferably, the deposition treatment time of 3h can achieve better experimental effects.

[0046] The application also provides an application of the CMS carbon molecular sieve prepared from the flower mud waste, and the CMS carbon molecular sieve prepared by the above preparation method is used for nitrogen separation.

[0047] The application will be further described below Figure 1 and examples, but not limit the scope of the application.

[0048] When the embodiments give a numerical range, it should be understood that, unless otherwise stated in the application, each numerical range of both ends and any one numerical value between the two ends can be selected. Unless otherwise defined, all technical and scientific terms used in the application have the same meaning as understood by those skilled in the art. Unless otherwise noted in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. All reagents or instruments, unless otherwise noted, are conventional products that can be obtained by commercial purchase. In addition to the specific methods, equipment, materials used in the examples, based on the mastery of the prior art by those skilled in the art and the description of the present application, any method, equipment and material of the prior art similar or equivalent to the method, equipment and material described in the examples of the present application can also be used to realize the present application.

[0049] Example 1 The method for preparing CMS carbon molecular sieve from flower soil waste in this embodiment includes the following steps: 1) The phenolic resin flower soil is crushed by a crusher, and a small amount of broken dust (G1) is generated in the process. The crushed material is dried by a dryer, and the drying temperature is 150°C. The material is fed into the drum by a feeding device. The high-temperature flue gas generated by the incinerator reciprocates in the pipe outside the drum. The material is continuously lifted and scattered under the action of the lifter plate to realize heat exchange in a spiral advancing manner, so that the water is continuously evaporated, and the material is dried. The drying time is about 1.5h. A small amount of dust (G2) is generated during the drying process. The crystal ball of the dried material is ground into a powder to form a precursor with a particle size of 5-30μm. The precursor is transported to a storage tank by a pipeline for storage. Ball milling dust (G3) is generated during the grinding process. The ground material is subjected to secondary drying for 1h. A small amount of dust (G4) is generated at the end of the dryer. The final precursor has a water content of 5-8%. A small amount of free formaldehyde, phenols and water vapor generated during the two drying processes are collected by pipeline condensation and then sent to the extrusion molding section for reuse. The ash content of the precursor in this embodiment is 2.68%, the volatile content is 40.32%, the moisture content is 5.82%, and the fixed carbon content is 51.18%; 2) 3kg of precursor, 100g of starch, 50g of coke oil, 50g of pitch and appropriate amount of water are stirred. A small amount of dust (G5) is generated during the stirring process. The uniformly mixed material is fed into an automatic temperature-controlled kneader. After uniform kneading by the kneader, the material is extruded into a carbonized material by a double-screw extruder. The purpose of mixing and kneading is to make the carbonized material have certain viscosity and prevent organic waste gas from volatilizing. The kneader is sealed with a cover. A small amount of organic waste gas is volatilized (Gu1) during the operation of the kneader; 3) The carbonized material is taken into the cylinder of the carbonization furnace by batch, the cylinder is rotated and continuously heated by resistance wire, and the components such as groups, bridges, free radicals and aromatic rings in the material are decomposed and polymerized during the pyrolysis process, and the generated heat unstable components are removed in the form of volatile matter, the purpose is to develop the pore of the carbonized product, and the pore size is expanded or shrunk; the carbonization process is divided into three stages: the first stage is 0-300℃, the exhaust gas is mainly water vapor, containing a small amount of low-carbon organic matter and part of volatile organic matter; the second stage is 300-650℃, the exhaust gas is mainly multi-carbon organic matter, which can self-ignite, and can be combusted violently with the aid of air to generate high temperature; the third stage is 650-850℃, the exhaust gas is mainly H2 and CO generated by the decomposition of the material, which can self-ignite, and the carbonization time is about 4h; After the carbonization is completed, the deposition treatment is carried out in the deposition furnace, and the temperature is raised to 800℃ under the protection of nitrogen, and pure benzene is introduced at a speed of 35g / min to adjust the pore, the dropping time is 30min, and the introduced benzene is rapidly decomposed into C and H mixture at high temperature, and C is deposited on the pore wall of the material, thereby reducing the pore diameter of the product. H and C can form CH4 gas, a small amount of benzene steam in the exhaust gas, and the deposition time is about 2.5h, and the product is obtained; The exhaust gas of the first stage of the carbonization process is mainly water vapor and VOC; due to the high temperature in the second and third stages, VOC and the like are all cracked into H2, CO, methane and the like. Methane and a small amount of VOC are generated during the deposition process. The VOC and other pollutants (G7) generated during the carbonization and deposition process are collected through a pipeline and then burned in the main incinerator, the combustion completion rate is more than 90%, and then enters the regenerative dust removal chamber, is subjected to the first dust removal, and then enters the auxiliary combustion furnace for residual exhaust gas incineration, and then is cooled through a water cooling tower, and is discharged through a 15m high exhaust gas cylinder (G8) after reaching the standard (G8), and the cooling water is recycled and added regularly. A large amount of waste heat generated during combustion is provided to the raw material drying system through a hot air conveying pipeline to provide indirect heating heat. The main incinerator uses 0# diesel oil as the combustion-supporting fuel, and the auxiliary combustion furnace uses biomass particles as the auxiliary fuel, and after secondary combustion, the exhaust gas combustion rate is more than 98%. Due to the fact that the equipment cannot be in an ideal state of being airtight, a small amount of unorganized volatile gas (Gu2) is generated during the carbonization and deposition process. A gas collecting hood is arranged above the carbonization furnace and the deposition furnace, and the unorganized volatile gas is collected by an induced draft fan and then absorbed by a water spraying device in the workshop, and then discharged to the atmosphere through a 15m high exhaust gas cylinder; After the deposition is completed, the discharged material is subjected to inspection and screening, the particle size is controlled to be about 1-1.5mm, the qualified product enters the warehouse, and the substandard product returns to the repeated deposition process. According to the enterprise experience data, the qualified rate of one-time deposition is generally 85%, and the qualified rate of two-time deposition is basically 100%. The dust (G6) generated during the screening process is collected by a bag dust collector.

[0050] Example 2 The method for preparing CMS carbon molecular sieve from the flower soil recycling waste material of the embodiment comprises the following steps: 1) The phenolic resin clay is crushed by a crusher, which generates a small amount of broken dust (G1) during the process. The crushed material is dried by a dryer at a temperature of 200°C. The material is fed into the drum by a feeding device. The high-temperature flue gas generated by the incinerator is circulated in the pipe outside the drum. The material is continuously lifted and scattered by the lifter plate to achieve heat exchange in a spiral advancing manner, so that the moisture is continuously evaporated, and the material is dried. The drying time is about 1.5 h. A small amount of dust (G2) is generated during the drying process. The dried material is ground into a powder by a ball mill to form a precursor material with a particle size of 5-30 μm. The precursor material is transported to a storage tank by a pipeline for storage. Ball mill dust (G3) is generated during the grinding process. The ground material is subjected to secondary drying for 1 h. A small amount of dust (G4) is generated at the end of the dryer. The final precursor material has a water content of 5-8%. A small amount of free formaldehyde, phenol and water vapor generated during the two drying processes is collected by condensation and sent to the extrusion molding section for reuse. The ash content of the precursor material of this embodiment is 2.68%, the volatile content is 40.32%, the moisture content is 5.82%, and the fixed carbon content is 51.18%; 2) 3 kg of precursor material, 100 g of starch, 50 g of coke oil, 50 g of pitch and an appropriate amount of water are stirred, which generates a small amount of dust (G5) during the stirring process. The uniformly mixed material is fed into an automatic temperature-controlled kneader. After uniform kneading by the kneader, the material is extruded into a carbonized material by a double-screw extruder. The purpose of mixing and kneading is to make the carbonized material have a certain viscosity and prevent the volatilization of organic waste gas. The kneader is sealed with a cover. A small amount of organic waste gas is volatilized (Gu1) during the operation of the kneader. 3) The carbonized material is fed into the cylinder of the carbonization furnace in batches. The cylinder is rotated and continuously heated by the resistance wire. The components such as groups, bridges, free radicals and aromatic rings in the material decompose and polymerize during the pyrolysis process, and the thermal unstable components are removed in the form of 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°C, the waste gas is mainly water vapor, containing a small amount of low-carbon organic matter and part of volatile organic matter; the second stage is 300-650°C, the discharged waste gas is mainly multi-carbon organic matter, which can self-ignite and can be burned vigorously with the aid of air to produce high temperature; the third stage is 650-850°C, the discharged waste gas is mainly H2 and CO, which can self-ignite. The carbonization time is about 5 h. After carbonization, the material is subjected to deposition treatment in a deposition furnace. The temperature is raised to 800°C under the protection of nitrogen. Pure benzene is introduced at a speed of 35 g / min to adjust the pore size. The benzene is rapidly decomposed into a mixture of C and H at high temperature, and C is deposited on the pore walls of the material, thereby reducing the pore diameter of the product. H and C can form CH4 gas, and a small amount of benzene vapor is discharged. The deposition time is about 3.5 h. The first stage of the carbonization process exhaust gas is mainly water vapor and VOCs; the second and third stages have high temperatures, and VOCs and the like are all cracked into H2, CO, methane and the like. Methane and a small amount of VOCs are generated during the deposition process. The VOCs and the like pollutants (G7) generated during the carbonization and deposition processes are collected through a pipeline and then burned in a main incinerator, with a combustion completion rate of 90% or more, and then enter a regenerative dust removal chamber, pass through the first dust removal, and then enter an auxiliary combustion furnace for residual exhaust gas incineration, and then pass through a water cooling tower for cooling, and then pass through a 15m high exhaust gas chimney for standard emission (G8), and the cooling water is recycled and added regularly. A large amount of heat generated during combustion is provided to the raw material drying system through a hot air conveying pipeline to provide indirect heating energy. The main incinerator uses 0# diesel as a combustion fuel, and the auxiliary combustion furnace uses biomass particles as an auxiliary fuel, and after secondary combustion, the exhaust gas combustion rate is 98% or more. The carbonization and deposition processes cannot be in an ideal state of airtightness due to equipment limitations, and therefore a small amount of unorganized volatile gas (Gu2) is generated. A gas collection hood is arranged above the carbonization furnace and the deposition furnace, and the unorganized volatile gas is collected by an induced draft fan and then absorbed by a water spraying device in the workshop, and then discharged to the atmosphere through a 15m high exhaust gas chimney. After the deposition is completed, the discharged material is inspected and sieved to control the sieved particle size to be about 1-1.5mm, and the qualified products are put into a warehouse, and the substandard products are returned to the repeated deposition process. According to the experience data of the enterprise, the qualified rate of one-time deposition is 85%, and the qualified rate of two-time deposition is basically 100%. The dust (G6) generated during the sieving process is collected by a bag dust collector.

[0051] Example 3 The method for preparing CMS carbon molecular sieve from the flower soil waste material in this example comprises the following steps: 1) The phenolic resin clay is crushed by a crusher, and a small amount of broken dust (G1) is generated in the process. The crushed material is dried by a dryer at a temperature of 200 DEG C. The material is fed into the roller by a feeding device. The high-temperature flue gas generated by the incinerator reciprocates in the pipe outside the roller. The material is continuously lifted and scattered by the lifter plate to realize heat exchange in a spiral advancing mode, so that the moisture is continuously evaporated, and the material is dried. The drying time is about 1.5 h. A small amount of dust (G2) is generated during the drying process. The dried material is ground into a micropowder by a ball mill to form a precursor material with a particle size of 5-30 μm. The precursor material is transported to a storage tank by a pipeline for storage. Ball mill dust (G3) is generated during the grinding process. The ground material is subjected to secondary drying for 1 h. A small amount of dust (G4) is generated at the end of the dryer. The final precursor has a moisture content of 5-8%. A small amount of free formaldehyde, phenols and water vapor generated during the two drying processes are collected by pipeline condensation and sent to the extrusion molding section for reuse. The ash content of the precursor material of this embodiment is 2.68%, the volatile content is 40.32%, the moisture content is 5.82%, and the fixed carbon content is 51.18%; 2) 3 kg of precursor material, 100 g of starch, 50 g of coke oil, 50 g of pitch, 50 g of interface agent and appropriate amount of water are stirred, and a small amount of dust (G5) is generated during the stirring process. The mixed and uniform material is fed into an automatic temperature control kneader. After uniform kneading by the kneader, the carbonized material is extruded and formed by a double screw extruder. The purpose of mixing and kneading is to make the carbonized material have certain viscosity and prevent organic waste gas from volatilizing. The kneader is sealed with a cover. A small amount of organic waste gas is volatilized (Gu1) during the operation of the kneader. The interface agent of this embodiment is prepared by the following steps: S1: 50 g of glycerol, 20 g of choline chloride and 10 g of water are mixed uniformly, then 5 g of N-(2-hydroxyethyl) acrylamide and 0.5 g of sodium chloride are added, and the mixture is stirred and dissolved to obtain a pre-liquid; S2: A photoinitiator is added to the pre-liquid (the amount of N-(2-hydroxyethyl) acrylamide is 1.5%), and a photopolymerization reaction is carried out at room temperature for 2 h under the condition of ultraviolet light with a wavelength of 365 nm and a power of 36 w to obtain the interface agent. 3) The carbonized material is taken into the barrel of the carbonization furnace by batch, the barrel is rotated and continuously heated by resistance wire, and the components such as groups, bridges, free radicals and aromatic rings in the material are decomposed and polymerized during the pyrolysis process, and the generated heat unstable components are removed in the form of volatile matter, the purpose is to develop the pores of the carbonized product, and the pore size is expanded or shrunk; the carbonization process is divided into three stages: the first stage is 0-300℃, the exhaust gas is mainly water vapor, containing a small amount of low-carbon organic matter and part of volatile organic matter; the second stage is 300-650℃, the exhaust gas is mainly multi-carbon organic matter, which can self-ignite, and can burn violently with the aid of air to produce high temperature; the third stage is 650-850℃, the exhaust gas is mainly H2 and CO generated by the decomposition of the material, which can self-ignite, and the carbonization time is about 4h; After carbonization, the product is subjected to deposition treatment in a deposition furnace, and is heated to 800℃ under the protection of nitrogen, and pure benzene is introduced at a speed of 35g / min to adjust the pore size, the dropping time is 30min, the introduced benzene is rapidly decomposed into C and H mixture at high temperature, and C is deposited on the pore wall of the material, thereby reducing the pore diameter of the product. H and C can form CH4 gas, and a small amount of benzene vapor in the exhaust gas, the deposition time is about 3h, and the product is obtained; The exhaust gas of the first stage of the carbonization process is mainly water vapor and VOC; due to the high temperature in the second and third stages, VOC and the like are all cracked into H2, CO, methane and the like. Methane and a small amount of VOC are generated during the deposition process. The VOC and other pollutants (G7) generated during the carbonization and deposition process are collected through a pipeline and then burned in a main incinerator, the combustion completion rate is more than 90%, and then enters a regenerative dust removal chamber, after the first dust removal, enters an auxiliary combustion furnace for residual exhaust gas incineration, and then is cooled by a water cooling tower, and is discharged (G8) through a 15m high exhaust gas cylinder after reaching the standard, the cooling water is recycled and added regularly. A large amount of waste heat generated during combustion is provided to the raw material drying system through a hot air conveying pipeline to provide indirect heating heat. The main incinerator uses 0# diesel as combustion-supporting fuel, and the auxiliary combustion furnace uses biomass particles as auxiliary fuel, and after secondary combustion, the exhaust gas combustion rate is more than 98%. Due to the fact that the equipment cannot be sealed in an ideal state, a small amount of unorganized volatile gas (Gu2) is generated during the carbonization and deposition process. A gas collecting hood is arranged above the carbonization furnace and the deposition furnace, and the unorganized volatile gas is collected by an induced draft fan and then absorbed by a water spraying device in the workshop, and then discharged to the atmosphere through a 15m high exhaust gas cylinder; After the deposition is completed, the discharged material is subjected to inspection and screening, the particle size is controlled to be about 1-1.5mm, the qualified product enters the warehouse, and the substandard product returns to the repeated deposition process. According to the experience data of the enterprise, the qualified rate of one-time deposition is generally 85%, and the qualified rate of two-time deposition is basically 100%. The dust (G6) generated during the screening process is collected by a bag dust collector.

[0052] Performance test The product performance is tested according to the standard HG / T 4364-2012, and the test results are shown in Table 1.

[0053] Although the present application has been described in detail with reference to the foregoing embodiments, the technical solutions recorded in the foregoing embodiments can be modified, or some of the technical features can be replaced by equivalent features, by those skilled in the art, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing CMS carbon molecular sieve from floral foam recycling waste, characterized in that: The method comprises the following steps: 1) crushing, grinding and drying phenolic resin clay to obtain a precursor; 2) mixing uniformly raw materials including the precursor, starch, coal tar, pitch and water, and extruding to obtain carbonized material; 3) carbonizing and depositing the carbonized material to obtain the CMS carbon molecular sieve.

2. The method of claim 1, wherein the method is characterized by: In the step 1), the particle size of the precursor is 5-30 μm.

3. The method of claim 1, wherein the method is characterized by: In the step 1), the water content of the precursor is 5-8%.

4. The method of claim 1, wherein the method is characterized by: In the step 1), the drying temperature is 150-200 ℃.

5. The method of claim 1, wherein the method is characterized by: In the step 2), an interface agent is added when uniformly mixing, and the interface agent is prepared by the following steps: S1: mixing glycerol, choline chloride and water uniformly, then adding N-(2-hydroxyethyl) acrylamide, and stirring to dissolve to obtain a front solution; S2: adding a photoinitiator to the front solution, and performing photopolymerization to obtain the interface agent.

6. The method of claim 1, wherein the method is characterized by: In the step 3), the carbonization comprises a first stage, a second stage and a third stage, the first stage is treated at 300 ℃, the second stage is treated at 300-650 ℃, and the third stage is treated at 650-850 ℃.

7. The method of claim 1, wherein the method is characterized by: In the step 3), the carbonization treatment time is 4-5 h.

8. The method of claim 1, wherein the method is characterized by: In the step 3), the deposition is performed by heating to 800-850 ℃ under nitrogen protection, and then pure benzene is introduced for deposition treatment.

9. The method of claim 1, wherein the method is characterized by: In the step 3), the deposition treatment time is 2.5-3.5 h.

10. The use of floral foam recycling waste to prepare CMS carbon molecular sieve, characterized in that: The CMS carbon molecular sieve prepared by the preparation method of any one of claims 1-9 is used in the field of gas separation.

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