Heteroatom-doped high-performance adsorption resin and preparation method thereof

Abstract

A preparation method of the adsorbent resin comprises the following steps: S1, mixing acrylonitrile, vinylpyridine, divinylbenzene and a pore-foaming agent to prepare an oil-phase mixture, dispersing a microporous template agent in a polyvinyl alcohol aqueous solution to prepare a water-phase mixture, uniformly mixing the water-phase mixture and the oil-phase mixture, introducing nitrogen, then adding azodiisobutyronitrile, and uniformly stirring to obtain a mixture; uniformly dispersing to obtain a copolymerization mixture; s2, sequentially carrying out heating prepolymerization on the copolymerization mixture, and then continuously carrying out heating reaction to obtain a polymerization intermediate product; s3, performing heat treatment, washing and vacuum drying on the polymerization intermediate product under the protection of nitrogen to obtain the high-performance adsorption resin.

Description

Technical Field

[0001] This application relates to an adsorption resin, and more specifically, to a heteroatom-doped high-performance adsorption resin and a method for preparing the same. Background Technology

[0002] With the upgrading of global industrial emission reduction demands, the need for carbon dioxide emission reduction has also increased. Carbon dioxide capture, utilization, and storage technologies have become one of the important means of controlling greenhouse gas emissions. However, CO2 is often generated in high-temperature environments, and traditional adsorption resins have insufficient temperature resistance. Resins with polystyrene or polyacrylonitrile as the basic framework and the introduction of amino groups are difficult to achieve efficient capture at high temperatures due to amino oxidation and framework softening. Resins with high-temperature resistant polymers such as polyimide and polyetheretherketone as the framework generally have low adsorption capacity and cannot meet the requirements for efficient capture.

[0003] Therefore, it is of great technical necessity and value to provide a carbon dioxide adsorption resin that has high adsorption capacity and selectivity and can meet the needs of more complex and demanding application scenarios. Summary of the Invention

[0004] In order to prepare a stable, efficient, and highly selective adsorption resin, this application provides a heteroatom-doped high-performance adsorption resin and its preparation method.

[0005] In a first aspect, this application provides a method for preparing a heteroatom-doped high-performance adsorption resin, comprising the following preparation steps: S1. Acrylonitrile, vinylpyridine, divinylbenzene and pore-forming agent are mixed to prepare an oil phase mixture, and a microporous template agent is dispersed in a polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture. The aqueous phase mixture and the oil phase mixture are mixed evenly, nitrogen gas is introduced, and then azobisisobutyronitrile is added and dispersed evenly to obtain a copolymer mixture. S2. The copolymer mixture is heated and prepolymerized sequentially, and then the temperature is increased to react and obtain the polymerization intermediate. S3. The polymerization intermediate is heat-treated under nitrogen protection, washed with water, and vacuum dried to obtain a high-performance adsorption resin.

[0006] By adopting the above scheme, the nitrogen-rich monomer is used as the precursor of the nitrogen active site, acrylonitrile contains a cyano group, and vinylpyridine contains a pyridine ring, both of which are high-nitrogen-content monomers, which can ensure the uniform distribution of nitrogen elements in the resin matrix, provide sufficient source for subsequent activation as CO2 adsorption sites, and use divinylbenzene as a 'linker' for the three-dimensional skeleton. Its molecule contains two double bonds, which can undergo radical copolymerization with the double bonds of the nitrogen-rich monomer to form a cross-linked three-dimensional polymer network. The network structure is stable, so that the obtained resin is not easy to swell or collapse during subsequent heating or adsorption. By adding a certain amount of microporous template agent to physically occupy and be wrapped by the polymer during polymerization, the inter-particle gap and surface form reserved channels, which can accurately control the pore size and provide channels for the molecular diffusion of carbon dioxide, and have high adsorption capacity and selectivity. Through gradient temperature control of low-temperature pre-polymerization and high-temperature curing, the nitrogen-rich monomer is gradually cross-linked to form a loose cross-linked network under lower radical concentration, the distribution of nitrogen sites is adjusted, and the nitrogen precursor is heat-treated under nitrogen protection to rearrange the structure and convert into pyrrole and pyridine type nitrogen with strong interaction with CO2. The prepared adsorption resin has high thermal stability and is more suitable for use in high-temperature scenes.

[0007] Preferably, the mass ratio of acrylonitrile to vinylpyridine is (2.5-3.5):1.0.

[0008] By limiting the mass ratio of acrylonitrile to vinylpyridine, the structure of the cross-linked network is further optimized, the content of pyrrole and pyridine type nitrogen is reasonable, the adsorption selectivity is high, and the temperature adaptability is wider.

[0009] Preferably, the heating pre-polymerization temperature is 50-60℃, the pre-polymerization time is 1.5-2.5 hours, the elevated temperature reaction temperature is 80-90℃, and the reaction time is 6-8 hours.

[0010] By controlling the preparation process, the rearrangement effect is good, the cyano group and the pyridine ring are converted into pyrrole and pyridine type nitrogen active sites, the quadrupole moment effect on carbon dioxide is enhanced, the heteroatom doping effect is good, and the through micropores have good selectivity for carbon dioxide.

[0011] Preferably, the heat treatment temperature is 240-260℃, and the treatment time is 1.0-1.2 hours.

[0012] At this time, the conversion effect of the cyano group and the pyridine ring and the thermal rearrangement effect of PVP are good, and the obtained adsorption resin has rich internal active sites and channels.

[0013] Preferably, the microporous template agent comprises PVP filled defect framework material, and the preparation steps comprise: adding zirconium tetrachloride, 2-amino terephthalic acid, and trifluoroacetic acid into DMF, ultrasonic dispersion, adding PVP, heating and stirring until uniform, increasing the temperature for reaction, cooling and centrifugation, washing, and vacuum drying to obtain the PVP filled defect framework material.

[0014] The PVP filled defect framework material prepared by the above preparation steps has abundant Zr 4 +, which can capture carbon dioxide through coordination, and through the competition between a certain amount of trifluoroacetic acid and 2-amino terephthalic acid, a certain defect is formed, leaving more abundant carbon dioxide channels and active sites, and PVP is fully infiltrated. The PVP in the product can be rearranged after heat treatment, exposing more reserved through holes and adsorption sites of the defect framework material, and can also form intermolecular hydrogen bonds with the pyridine ring of the resin, together enhancing the adsorption selectivity of carbon dioxide. The pyrrolidone ring is tightly anchored to the resin through π-π stacking with the benzene ring and pyridine ring of the resin matrix and polar interaction after thermal rearrangement, so that the PVP filled defect framework material is more uniformly and tightly distributed in the matrix after heat treatment, and the combined effect of the multi-level pores and multiple types of sites is good. After thermal rearrangement, the selectivity of the prepared adsorption resin is further improved due to the more sufficient exposure of the nitrogen-containing polar group.

[0015] Preferably, the mass ratio of 2-amino terephthalic acid to trifluoroacetic acid in the preparation steps is (9-12):5.

[0016] The competition effect of trifluoroacetic acid and 2-amino terephthalic acid is appropriate, occupying part of the coordination sites of Zr clusters to form a certain coordination defect site, expanding the pore volume and increasing the specific surface area, and after the addition of PVP, the PVP is combined with the defect site, and the PVP forms a certain rearrangement during subsequent heat treatment, continuing to expose the reserved defect channels, and the prepared adsorption resin has better selectivity and adsorption performance due to the size of the defect channels being more suitable for the diffusion of carbon dioxide.

[0017] Preferably, the stirring speed is 600-900 rpm.

[0018] Preferably, the molecular weight of PVP is 5000-15000.

[0019] Preferably, the mass ratio of PVP filled defect framework material to divinylbenzene is less than or equal to 1:4.

[0020] The applicant finds that the addition of PVP filling defect framework material significantly improves the adsorption capacity and selectivity, performance stability of the resin, but when the addition amount is greater than 1 / 4 of divinylbenzene, a certain agglomeration of PVP filling defect framework material may occur, and the connectivity of the pore channels of the resin matrix is affected, the performance improvement starts to be not significant and gradually produces negative effects.

[0021] In a second aspect, the application provides a heteroatom-doped high-performance adsorption resin prepared by the above preparation method.

[0022] In summary, the application has the following beneficial effects: The application provides a preparation method of a heteroatom-doped high-performance adsorption resin, which has fewer preparation steps and large adsorption capacity. By adding a certain amount of acrylonitrile, vinylpyridine and divinylbenzene for copolymerization and thermal conversion to form abundant active sites, the adsorption resin has higher thermal stability and carbon dioxide selectivity compared with traditional adsorption resins, and is suitable for flue gas treatment, closed space gas purification and other complex scenes.

[0023] The application further improves the active sites and specific surface area of the adsorption resin by adding a certain amount of PVP filling defect framework material, and by reserving certain defects and filling PVP for rearrangement, further releasing the pore channels and active sites and participating in crosslinking. Compared with traditional microporous templates, the performance improvement is more significant, and the interface combination is more stable. DETAILED DESCRIPTION

[0024] To further help understand the technical solutions of the application, several specific embodiments are provided to describe the technical solutions of the application in more detail. All the described embodiments are only part of the embodiments of the application, not all. Embodiments can be combined with each other, and the same or similar concepts or processes may not be described again in some embodiments. The following embodiments are further descriptions of the application, and the application is not limited thereto.

[0025] The remaining experimental reagents, unless otherwise specified, are conventional commercially available brands or obtained by conventional preparation processes.

[0026] Nanosilica was purchased from Guangzhou Shenna Trade Co., Ltd. SHENNA 200. PVP K15 and PVP K30 were purchased from JUNBIKE.

[0027] Preparation Example Preparation Example 1: Framework material: To 2.33 g of zirconium tetrachloride, 1.81 g of 2-amino terephthalic acid, 1.0 ml of trifluoroacetic acid in 300 ml of DMF, 300 W ultrasonic dispersion for 20 min, 80°C stirring for 4 hours, heating to 120°C for 24 hours, cooling and centrifugation, DMF washing 3 times, water washing 3 times, 80°C vacuum drying for 12 hours to obtain a defective framework material.

[0028] Preparation Example 2: Defective framework material To 2.33 g of zirconium tetrachloride, 1.81 g of 2-amino terephthalic acid, 1.0 ml of trifluoroacetic acid in 300 ml of DMF, 300 W ultrasonic dispersion for 20 min, 80°C stirring for 4 hours, heating to 120°C for 24 hours, cooling and centrifugation, DMF washing 3 times, water washing 3 times, 80°C vacuum drying for 12 hours to obtain a defective framework material.

[0029] Preparation Example 3: Defective framework material To 2.33 g of zirconium tetrachloride, 1.81 g of 2-amino terephthalic acid, 1.5 ml of trifluoroacetic acid in 300 ml of DMF, 300 W ultrasonic dispersion for 20 min, 80°C stirring for 4 hours, heating to 120°C for 24 hours, cooling and centrifugation, DMF washing 3 times, water washing 3 times, 80°C vacuum drying for 12 hours to obtain a defective framework material.

[0030] Preparation Example 4: PVP filled defective framework material To 2.33 g of zirconium tetrachloride, 1.81 g of 2-amino terephthalic acid, 1.0 ml of trifluoroacetic acid in 300 ml of DMF, 300 W ultrasonic dispersion for 20 min, 80°C stirring for 4 hours, heating to 120°C for 24 hours, cooling and centrifugation, DMF washing 3 times, water washing 3 times, 80°C vacuum drying for 12 hours to obtain a defective framework material.

[0031] Preparation Example 5: PVP filled defective framework material To 2.33 g of zirconium tetrachloride, 1.81 g of 2-amino terephthalic acid, 1.0 ml of trifluoroacetic acid in 300 ml of DMF, 300 W ultrasonic dispersion for 20 min, 80°C stirring for 4 hours, heating to 120°C for 24 hours, cooling and centrifugation, DMF washing 3 times, water washing 3 times, 80°C vacuum drying for 12 hours to obtain a defective framework material. Example

[0032] Example 1 S1, 60 g of acrylonitrile, 20 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 5 g of nano-silica was dispersed in 500 ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, nitrogen was introduced for 30 min to remove oxygen, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, then continued to be heated to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol for 3 times, heated to 250°C at a rate of 3°C / min, and kept for 1 hour, then washed with water to neutral, and vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0033] Example 2 S1, 40 g of acrylonitrile, 40 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 5 g of nano-silica was dispersed in 500 ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, nitrogen was introduced for 30 min to remove oxygen, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, then continued to be heated to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol for 3 times, heated to 250°C at a rate of 3°C / min, and kept for 1 hour, then washed with water to neutral, and vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0034] Example 3 S1, 60 g of acrylonitrile, 20 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 5 g of nano-silica was dispersed in 500 ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, nitrogen was introduced for 30 min to remove oxygen, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, then continued to be heated to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol for 3 times, heated to 250°C at a rate of 3°C / min, and kept for 1 hour, then washed with water to neutral, and vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0035] Example 4 S1. 60g acrylonitrile, 20g vinylpyridine, 20g divinylbenzene and 50ml n-heptane were mixed to prepare an oil phase mixture. 5g of the PVP defect-filling framework material prepared in Preparation Example 4 was dispersed in 500ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture. The aqueous phase mixture and the oil phase mixture were mixed evenly at 300rpm. Nitrogen gas was introduced for 30min to remove oxygen. Then 1g azobisisobutyronitrile was added and stirring was continued for 30min to obtain a copolymer mixture. S2. React the copolymer mixture in a 60°C water bath for 2 hours, then continue to heat to 80°C and react for 8 hours to obtain the polymerization intermediate. S3. Wash the polymerization intermediate with ethanol three times, heat it to 280°C at 3°C / min, keep it at that temperature for 1 hour, wash it with water until neutral, and vacuum dry it at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0036] Example 5 S1. 60g acrylonitrile, 20g vinylpyridine, 20g divinylbenzene and 50ml n-heptane were mixed to prepare an oil phase mixture. 5g of the framework material prepared in Preparation Example 1 was dispersed in 500ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture. The aqueous phase mixture and the oil phase mixture were mixed evenly at 300rpm. Nitrogen gas was introduced for 30min to remove oxygen. Then 1g azobisisobutyronitrile was added and stirring was continued for 30min to obtain a copolymer mixture. S2. React the copolymer mixture in a 60°C water bath for 2 hours, then continue to heat to 80°C and react for 8 hours to obtain the polymerization intermediate. S3. Wash the polymerization intermediate with ethanol three times, heat it to 250°C at 3°C / min, keep it at that temperature for 1 hour, wash it with water until neutral, and vacuum dry it at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0037] Example 6 S1. 60g acrylonitrile, 20g vinylpyridine, 20g divinylbenzene and 50ml n-heptane were mixed to prepare an oil phase mixture. 5g of the defect framework material prepared in Preparation Example 2 was dispersed in 500ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture. The aqueous phase mixture and the oil phase mixture were mixed evenly at 300rpm. Nitrogen gas was introduced for 30min to remove oxygen. Then 1g azobisisobutyronitrile was added and stirring was continued for 30min to obtain a copolymer mixture. S2. React the copolymer mixture in a 60°C water bath for 2 hours, then continue to heat to 80°C and react for 8 hours to obtain the polymerization intermediate. S3. Wash the polymerization intermediate with ethanol three times, heat it to 250°C at 3°C / min, keep it at that temperature for 1 hour, wash it with water until neutral, and vacuum dry it at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0038] Example 7 S1, 60 g of acrylonitrile, 20 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 5 g of the defect framework material prepared in Preparation Example 3 was dispersed in 500 ml of a 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, nitrogen was introduced for 30 min to remove oxygen, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, then the temperature was continuously increased to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol 3 times, the temperature was increased to 250°C at a rate of 3°C / min, and the temperature was maintained for 1 hour, then water was added to neutralize, and the product was vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0039] Example 8 S1, 60 g of acrylonitrile, 20 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 5 g of the defect framework material prepared in Preparation Example 3 was dispersed in 500 ml of a 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, nitrogen was introduced for 30 min to remove oxygen, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, then the temperature was continuously increased to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol 3 times, the temperature was increased to 250°C at a rate of 3°C / min, and the temperature was maintained for 1 hour, then water was added to neutralize, and the product was vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0040] Example 9 S1, 60 g of acrylonitrile, 20 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 5 g of the defect framework material prepared in Preparation Example 3 was dispersed in 500 ml of a 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, nitrogen was introduced for 30 min to remove oxygen, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, then the temperature was continuously increased to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol 3 times, the temperature was increased to 250°C at a rate of 3°C / min, and the temperature was maintained for 1 hour, then water was added to neutralize, and the product was vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0041] Example 10 S1, 60 g of acrylonitrile, 20 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 10 g of PVP filled defect framework material prepared in preparation example 5 was dispersed in 500 ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, oxygen was removed by passing nitrogen for 30 min, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, and then the temperature was continuously increased to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol for 3 times, the temperature was increased to 250°C at a rate of 3°C / min, and the temperature was kept for 1 hour, then water was washed to neutral, and the product was vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0042] Comparative Example Comparative Example 1 S1, 60 g of acrylonitrile, 20 g of vinylpyridine, 20 g of divinylbenzene, 50 ml of n-heptane were mixed to prepare an oil phase mixture, 10 g of PVP filled defect framework material prepared in preparation example 5 was dispersed in 500 ml of 5vt% polyvinyl alcohol aqueous solution to prepare an aqueous phase mixture, the aqueous phase mixture and the oil phase mixture were mixed uniformly at 300 rpm, oxygen was removed by passing nitrogen for 30 min, then 1 g of azobisisobutyronitrile was added, and stirring was continued for 30 min to obtain a copolymerization mixture; S2, the copolymerization mixture was reacted in a water bath at 60°C for 2 hours, and then the temperature was continuously increased to 80°C for 8 hours to obtain a polymerization intermediate product; S3, the polymerization intermediate product was washed with ethanol for 3 times, the temperature was increased to 250°C at a rate of 3°C / min, and the temperature was kept for 1 hour, then water was washed to neutral, and the product was vacuum dried at 60°C for 24 hours to obtain a high-performance adsorption resin.

[0043] Performance test test one: the performance of the adsorption resin prepared in the examples and the comparative examples was determined by dynamic adsorption. 5.000 g of resin was vacuum degassed, packed in a quartz fixed bed with an inner diameter of 10 mm and a length of 15 cm, the bed layer was fixed with quartz wool at both ends, the fixed bed was jacketed with a constant temperature jacket connected to a constant temperature water bath, the experimental temperature was controlled at 25°C, nitrogen was blown, then 100 mL·min-1 of 15vt% CO2 / N2 mixed gas was introduced at a constant flow rate, after the outlet CO2 concentration was stable, the gas volume concentration at the outlet end of the fixed bed through the adsorption resin was recorded by gas chromatography detection, and the CO2 adsorption amount (mmol·g-1) was calculated, that is, the millimoles of CO2 adsorbed per gram of resin.

[0044] Test two: the breakthrough time and adsorption amount of CO2 and N2 during test one were recorded, and the separation coefficient was calculated.

[0045] Test three: the prepared adsorption resin of the examples and comparative examples was placed in a damp heat test chamber, from room temperature 25℃, 50% relative humidity to 200℃, 80% relative humidity, and then to room temperature 25℃, 50% relative humidity, 72 minutes for one cycle, 50 times of damp heat cycle, and then the test one was repeated to calculate the retention rate of adsorption capacity.

[0046] The test results are summarized in Table 1.

[0047] Table 1 Adsorption amount / mmol g -1 ]] Separation coefficient Adsorption amount retention rate (%) Example 1 6.1 51 90.1 Example 2 6.0 49 89.4 Example 3 5.7 47 93.3 Example 4 6.3 52 93.1 Example 5 6.3 53 92.3 Example 6 6.7 55 93.7 Example 7 6.2 52 93.5 Example 8 6.9 61 96.5 Example 9 6.4 55 94.6 Example 10 5.7 50 89.7 Comparative Example 1 5.5 17 74.4 In combination with Examples 1-2, Comparative Example 1 and with reference to Table 1, the present application uses a certain mass ratio of acrylonitrile and vinylpyridine to participate in polymerization and heat treatment to prepare the adsorption resin, and the prepared adsorption resin has high selectivity for carbon dioxide and good performance retention effect after high temperature cycle.

[0048] In combination with Examples 3, 4 and 8 and with reference to Table 1, the present application limits the heat treatment temperature, so that not only acrylonitrile and vinylpyridine can achieve good conversion effect, but also PVP filled in the defect framework material can achieve good rearrangement, further releasing the reserved pore size and exposing more active groups, forming a closer connection with the matrix, and the prepared adsorption resin has better performance.

[0049] In combination with Examples 5-10 and with reference to Table 1, the present application further provides a preparation step of filling the defect framework material with PVP, and limits the competition degree of trifluoroacetic acid, the molecular weight of PVP and the amount of PVP filled in the defect framework material, so that the defect effect of the prepared framework material is appropriate, and the filling and releasing effect is more suitable for the absorption of carbon dioxide.

[0050] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A process for the preparation of a high performance adsorbent resin doped with a heteroatom, characterized in that: The preparation method comprises the following steps: S1, mixing acrylonitrile, vinylpyridine, divinylbenzene and a pore-forming agent to obtain an oil phase mixture, dispersing a microporous template in a polyvinyl alcohol aqueous solution to obtain an aqueous phase mixture, uniformly mixing the aqueous phase mixture and the oil phase mixture, introducing nitrogen, then adding azobisisobutyronitrile, and uniformly dispersing to obtain a copolymer mixture; S2, sequentially heating and pre-polymerizing the copolymer mixture, and then continuously heating and reacting to obtain a polymer intermediate product; S3, heat-treating the polymer intermediate product under nitrogen protection, washing with water, and vacuum drying to obtain a high-performance adsorption resin.

2. The process for the preparation of a high performance heteroatom doped adsorbent resin as claimed in claim 1, wherein: The mass ratio of acrylonitrile to vinylpyridine is (2.5-3.5):1.

0.

3. The process for the preparation of a high performance heteroatom doped adsorbent resin as claimed in claim 1, wherein: The pre-polymerization temperature is 50-60℃, the pre-polymerization time is 1.5-2.5 hours, the reaction temperature is 80-90℃, and the reaction time is 6-8 hours.

4. The process for the preparation of a heteroatom doped high performance adsorbent resin as claimed in claim 1, wherein: The heat treatment temperature is 240-260℃, and the treatment time is 1.0-1.2 hours.

5. The process for the preparation of a high performance heteroatom doped adsorbent resin as claimed in claim 1, wherein: The microporous template comprises a PVP filled defect framework material, and the preparation method comprises the following steps: adding zirconium tetrachloride, 2-amino terephthalic acid and trifluoroacetic acid into DMF, ultrasonic dispersion, adding PVP, heating and stirring uniformly, heating and reacting, cooling and centrifuging, washing and vacuum drying to obtain the PVP filled defect framework material.

6. The process for the preparation of a heteroatom doped high performance adsorbent resin as claimed in claim 5, wherein: The mass ratio of 2-amino terephthalic acid to trifluoroacetic acid in the preparation method is (9-12):

5.

7. The process for the preparation of a heteroatom doped high performance adsorbent resin as claimed in claim 5, wherein: The stirring speed is 600-900 rpm.

8. The process for the preparation of a heteroatom doped high performance adsorbent resin as claimed in claim 5, wherein: The molecular weight of the PVP is 5000-15000.

9. The process for the preparation of a heteroatom doped high performance adsorbent resin as claimed in claim 5, wherein: The mass ratio of the PVP filled defect framework material to divinylbenzene is less than or equal to 1:

4.

10. A high performance adsorbent resin doped with a heteroatom, characterized in that: The high-performance adsorption resin doped with heteroatoms is prepared by the method of any one of claims 1-9.