An unsaturated metal-amine-based coordination polymer carbon sequestration filler and a preparation method thereof

Abstract

The present application belongs to the technical field of carbon fixation filler, and particularly relates to an unsaturated metal-amine-based coordination polymer carbon fixation filler and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing a polymer mother liquor, unsaturated metal coordination polymer microcrystal powder and cellulose acetate according to a proportion to obtain slurry, wherein the polymer is an elastic polymer material; uniformly applying the slurry to the surface of a filler substrate, first gradiently increasing temperature for drying, and then vacuum deep drying, so that polymer chain segments are rearranged to form a three-dimensional network structure to obtain an intermediate; immersing the intermediate in an amine functionalized grafting treatment liquid, so that amine functional monomers in the amine functionalized grafting treatment liquid diffuse and are adsorbed to the inner surface of the coating channel; after the immersion is completed, vacuum drying is performed, and the temperature is gradually increased during the drying process. The elastic characteristics of the coating enable it to adapt to thermal expansion and contraction and slight deformation of the filler in the repeated adsorption-regeneration process, thereby guaranteeing long-term cycle stability.

Description

Technical Field

[0001] This invention belongs to the field of carbon fixation filler technology, specifically relating to an unsaturated metal-amine coordination polymer carbon fixation filler and its preparation method. Background Technology

[0002] The statements herein provide only background information in relation to this invention and do not necessarily constitute prior art.

[0003] As global carbon emission reduction targets are being pursued more deeply, the capture and storage of low-concentration carbon dioxide in scenarios such as natural gas, industrial flue gas, cement kiln exhaust gas, and direct air capture has become a key link in achieving carbon neutrality. These gas sources generally have characteristics such as low CO2 partial pressure (typically below 15 vol%), high moisture content, high oxygen content, and complex impurity composition, placing stringent requirements on the dynamic capture capacity, selectivity, and long-term operational stability of adsorption materials. Currently, decarbonization technologies for low-concentration CO2 gas sources mainly include amine absorption, membrane separation, and pressure swing adsorption.

[0004] While amine absorption is a mature technology, it suffers from high regeneration energy consumption, severe equipment corrosion, and solvent degradation. Membrane separation technology is limited by the trade-off between selectivity and permeability, making it difficult to guarantee separation accuracy under high-throughput conditions. Although pressure swing adsorption (PSA) offers operational flexibility, conventional adsorption materials exhibit poor stability under humid, low-concentration CO2 gas source conditions. Furthermore, the performance of the adsorption packing material directly determines the separation efficiency and energy consumption level. Therefore, developing high-performance adsorption packing materials suitable for low-concentration CO2 gas source conditions has become a research hotspot in the field of oil and gas field emission reduction.

[0005] Metal coordination polymers exhibit significant advantages in CO2 adsorption and separation due to their extremely high specific surface area, tunable pore structure, and abundant unsaturated metal coordination sites. Unsaturated metal coordination centers can form reversible interactions with CO2 molecules through coordination, achieving highly selective CO2 capture and maintaining high adsorption capacity even under low-concentration CO2 gas source conditions. However, metal coordination polymers are typically present in powder form, and their direct use as fixed-bed packing materials faces challenges such as high pressure drop, dust entrainment, bed blockage, and high engineering difficulty, hindering their practical application in oil and gas fields.

[0006] Loading metal coordination polymers onto the surface of structured or particulate packings to form coated fixed-bed packings is one of the effective ways to solve the challenges of powder engineering. Coating technology combines the high adsorption performance of metal coordination polymers with the low flow resistance of structured supports, achieving efficient and low-consumption CO2 capture. However, existing research on metal coordination polymer coated packings faces several challenges: traditional coatings are prone to cracking and peeling in industrial applications due to temperature fluctuations, airflow impacts, and loading / unloading operations, leading to decreased adsorption performance and shortened service life; simultaneously, film-forming materials or binders often clog the pores of the metal coordination polymer during coating preparation, reducing effective adsorption sites and affecting carbon fixation efficiency; furthermore, conventional coatings lack elasticity and adaptability, making it difficult to match the thermal and mechanical stresses in fixed-bed operation. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide an unsaturated metal-amine coordination polymer carbon filler and its preparation method.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution: In a first aspect, the present invention provides a method for preparing an unsaturated metal-amine coordination polymer carbon filler, comprising the following steps: After the polymer mother liquor, unsaturated metal coordination polymer microcrystalline powder and cellulose acetate are mixed evenly in a certain proportion, a slurry is obtained. The polymer is an elastic polymer material. The slurry is uniformly coated on the surface of the filler substrate, first dried by gradient heating, and then dried in vacuum to allow the polymer chain segments to rearrange and form a three-dimensional network structure, thus obtaining the intermediate. The intermediate is immersed in an amine functionalization grafting solution, which allows the amine functional monomers in the amine functionalization grafting solution to diffuse and adsorb onto the inner surface of the coating pores. After impregnation, it is vacuum dried, with the temperature gradually increased during the drying process.

[0009] Secondly, the present invention provides an unsaturated metal-amine coordination polymer carbon filler, which is prepared by the aforementioned preparation method.

[0010] Thirdly, the present invention provides the application of the unsaturated metal-amine coordination polymer carbon fixative filler as a carbon dioxide adsorbent.

[0011] The beneficial effects achieved by one or more embodiments of the present invention described above are as follows: In the preparation of carbon-fixing fillers, this invention uses an elastic polymer material as the film-forming matrix and introduces an unsaturated metal coordination polymer as a functional filler. By optimizing the interfacial compatibility and pore accessibility of the two materials, the coating achieves excellent elasticity, adhesion, and wear resistance while maintaining the high CO2 adsorption performance of the metal coordination polymer. Applying this coating to the surface of structured filler substrates such as ceramic honeycomb, metal mesh, and foam ceramics yields coated fixed-bed fillers with low flow resistance, high adsorption capacity, and good mechanical stability.

[0012] When CO2-containing natural gas flows through the packed bed, the CO2 is adsorbed and captured by the metal coordination polymer sites in the coating. After adsorption saturation, the bed is heated and regenerated using low-temperature waste heat (60-70℃) from the oilfield (such as compressor waste heat or associated gas combustion waste heat). The released enriched CO2 can be used for oil displacement or resource utilization. The elastic characteristics of the coating enable it to adapt to the thermal expansion and contraction and slight deformation of the packing during repeated adsorption-regeneration processes, ensuring long-term cycle stability. Attached Figure Description

[0013] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0014] Figure 1 This is a surface morphology diagram of the metal-amine coordination polymer solid carbon filler prepared in Example 2 of the present invention; Figure 2 Surface elemental analysis of the metal-amine coordination polymer carbon filler prepared in Example 2 of this invention; Figure 3 This is a comparison chart of adsorption performance under different ratios of polymer matrix and metal coordination polymer in the embodiments of the present invention; Figure 4 This is a comparison chart of the adsorption performance of different types of metal coordination polymers in the embodiments of the present invention; Figure 5 This is a cyclic stability diagram of the metal-amine coordination polymer carbon filler prepared in Example 2 of the present invention. Detailed Implementation

[0015] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0016] In a first aspect, the present invention provides a method for preparing an unsaturated metal-amine coordination polymer carbon filler, comprising the following steps: After the polymer mother liquor, unsaturated metal coordination polymer microcrystalline powder and cellulose acetate are mixed evenly in a certain proportion, a slurry is obtained. The polymer is an elastic polymer material. The slurry is uniformly coated on the surface of the filler substrate, first dried by gradient heating, and then dried in vacuum to allow the polymer chain segments to rearrange and form a three-dimensional network structure, thus obtaining the intermediate. The intermediate is immersed in an amine functionalization grafting solution, which allows the amine functional monomers in the amine functionalization grafting solution to diffuse and adsorb onto the inner surface of the coating pores. After impregnation, it is vacuum dried, with the temperature gradually increased during the drying process.

[0017] The polymer in the polymer mother liquor is an elastic polymer material. Its elasticity allows the coating to adapt to thermal expansion and contraction and slight deformation during the adsorption-regeneration process, ensuring long-term cycle stability. The elastic polymer material forms a three-dimensional network structure in the later stage, which serves as a carrier for the metal coordination polymer and cellulose acetate, avoiding problems such as large pressure drop and dust entrainment when the powder is used directly.

[0018] Unsaturated metal coordination polymer microcrystalline powder, as a functional adsorbent filler, selectively captures CO2. Unsaturated metal coordination polymers have a high specific surface area, adjustable pore structure, and unsaturated metal coordination sites. Through coordination, they form reversible interactions with CO2 molecules, achieving highly selective adsorption.

[0019] Cellulose acetate, as a pore structure guiding agent, can optimize the pores of the coating, avoid pore blockage caused by excessive accumulation of polymer segments during film formation, and ensure the full exposure of adsorption sites of metal coordination polymers. Cellulose acetate can also promote uniform dispersion of the slurry, improve the adhesion between the coating and the substrate, and ensure the mechanical strength and adsorption efficiency of the coating.

[0020] The elastic polymer material and cellulose acetate synergistically regulate the rheology of the slurry, ensuring uniform dispersion of the metal coordination polymer microcrystalline powder and avoiding agglomeration. During the vacuum drying process, the polymer chain segments rearrange to form a three-dimensional network, and cellulose acetate guides the formation of the pore structure, enabling the amine functional monomers to diffuse efficiently into the interior of the coating, further enhancing the CO2 adsorption sites.

[0021] After the slurry is evenly applied to the surface of the filler substrate, if it is directly dried at high temperature, the solvent (such as toluene or petroleum ether) will evaporate rapidly, causing the coating surface to harden quickly. However, the internal solvent cannot escape in time, which can easily lead to bubbles, cracks, or pore collapse. Gradient heating increases the temperature in stages, allowing the solvent to evaporate slowly, ensuring that the inside of the coating dries synchronously with the surface, and maintaining structural integrity.

[0022] Higher temperatures enhance the mobility of chain segments in elastic polymer materials. During gradual heating, these materials can slowly rearrange to form a stable three-dimensional network structure. However, if the temperature rises too quickly, the chain segments may not have enough time to arrange themselves in an orderly manner before the coating solidifies, potentially leading to a loose network structure and affecting the coating's mechanical strength and elasticity. The pore structure and unsaturated sites of unsaturated metal-coordinated polymer microcrystalline powders are highly sensitive to temperature. Gradient heating can prevent high temperatures from damaging their crystal structure, ensuring the integrity of adsorption sites and maintaining the CO2 adsorption capacity.

[0023] Amine functional monomers diffusely adsorb onto the inner surface of the coating pores, forming chemisorption interactions with CO2 molecules. This replenishes the unsaturated metal sites of the metal coordination polymer, significantly enhancing the overall adsorption capacity. The amine group exhibits a higher affinity for CO2 than other gases, enabling preferential CO2 capture from associated natural gas, thus addressing the issue of insufficient selectivity at single adsorption sites in metal coordination polymers.

[0024] The binding of amine functional monomers to the inner surface of the coating pores can inhibit the loss of metal coordination polymer microcrystalline powder. Furthermore, graft modification makes the carbon fixation filler more suitable for low-temperature regeneration, ensuring the filler's cyclic adsorption performance.

[0025] In some embodiments, the polymer matrix in the polymer mother liquor is styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), or polyisobutylene-styrene block copolymer (SIBS). All three elastomers have a hard-soft-hard triblock structure. The polystyrene hard segments act as physical crosslinking points, imparting good mechanical strength and structural stability to the coating, while the rubber-phase soft segments provide high elasticity and flexibility, allowing the coating to remain intact despite substrate deformation, thus avoiding the brittleness problem of traditional rigid MOF coatings. Addressing the shortcomings of amine MOFs, such as sensitivity to moisture and susceptibility to structural collapse or amine deactivation, the selected matrices all possess excellent hydrophobicity, providing a stable hydrophobic microenvironment for amine MOFs and significantly extending the coating's service life in humid environments. In addition, all three are readily soluble in conventional organic solvents, which is beneficial for the uniform dispersion of amine MOF particles. At the same time, the benzene ring structure in the polymer can form a weak interaction with the aromatic ligands or amine groups in the MOFs, enhancing the interfacial bonding force between the inorganic and organic phases and ensuring that the MOF particles are firmly anchored and not easily detached.

[0026] Preferably, the polymer matrix is ​​a styrene-isoprene-styrene block copolymer (SIS).

[0027] Preferably, the metal coordination polymer microcrystalline powder is selected from MIL-100 (Cr), UiO-66 (Zr) or MIL-100 (Fe) microcrystalline powder.

[0028] More preferably, the mass ratio of the polymer matrix, the metal coordination polymer microcrystalline powder, and cellulose acetate is 1-3:1-3:1.

[0029] The mass ratio of the polymer matrix to the metal-coordinated polymer microcrystalline powder is 1-3:1-2, more preferably 1-3:1, and even more preferably 1:1.

[0030] In some embodiments, the solvent in the polymer mother liquor is toluene, petroleum ether, or ethyl acetate.

[0031] Block copolymers such as SBS, SIS, and SIBS are nonpolar or weakly polar materials. Toluene (nonpolar), petroleum ether (nonpolar), and ethyl acetate (moderately polar) can interact with polymer segments through van der Waals forces to obtain stable polymer mother liquors. Solvent molecules penetrate into the polymer interior, weakening intermolecular forces and allowing the elastic polymer segments to stretch, providing good flowability for subsequent mixing with metal-coordinated polymers and cellulose acetate.

[0032] The three solvents have moderate boiling points and can be gradually evaporated by gradient heating, avoiding coating bubbles, cracks or pore collapse caused by rapid solvent evaporation.

[0033] Preferably, the polymer mother liquor is prepared by adding the polymer matrix components to a solvent and swelling them in a sealed water bath at a constant temperature to form a homogeneous polymer mother liquor.

[0034] In some embodiments, the polymer mother liquor, metal coordination polymer microcrystalline powder and cellulose acetate are mixed in proportion and then ultrasonically dispersed to obtain a slurry.

[0035] In some embodiments, the filler substrate is a ceramic honeycomb or corrugated ceramic.

[0036] Preferably, after the slurry is uniformly applied to the surface of the filler substrate, the resulting coating thickness is 200-500 μm.

[0037] In some embodiments, the gradient temperature drying method involves drying at 45-53°C, 57-63°C, and 67-72°C sequentially for 5-15 minutes. This allows the coating to gradually set and form an initial network structure.

[0038] In some embodiments, the temperature for vacuum deep drying is 65-75℃, the vacuum degree is -0.08 ~ -0.03MPa, and the drying time is 3-10h.

[0039] Preferably, the temperature for vacuum deep drying is 67-72℃, the vacuum degree is -0.08 ~ -0.05MPa, and the drying time is 5-10h.

[0040] The crystal structure and unsaturated metal sites of unsaturated metal coordination polymers are temperature-sensitive. High temperatures (>75°C) may cause coordination bond breakage or pore collapse, reducing CO2 adsorption capacity. Vacuum drying, through low-temperature conditions, can avoid such structural damage.

[0041] In a vacuum environment, the resistance to chain segment movement of elastic polymer materials decreases, making it easier to form a stable three-dimensional network structure through slow rearrangement. If the temperature is simply increased, the chain segments may move too fast, resulting in disordered accumulation, which affects the elasticity and mechanical strength of the coating.

[0042] A vacuum environment can isolate air, preventing the elastic polymer materials from oxidizing and degrading at high temperatures, while also avoiding the decomposition or cross-linking of amine functional monomers under high-temperature and aerobic conditions.

[0043] In some embodiments, the amine functional monomer in the amine-functionalized grafting solution is hydroxyethyl ethylenediamine, monoethanolamine, or diethanolamine. All three monomers contain bifunctional structures with both amine (-NH2 / -NH) and hydroxyl (-OH) groups, and their molecular sizes increase sequentially, exhibiting good matching with the pores and coordination unsaturated sites of amine MOFs.

[0044] Preferably, the amino functional monomer is hydroxyethyl ethylenediamine.

[0045] Preferably, the solvent in the amine functionalization grafting solution is an alcohol solvent.

[0046] In some embodiments, the intermediate is impregnated in an amine-functionalized grafting solution by shaking at 80-120 rpm, 20-30°C, for 2-4 hours.

[0047] In some embodiments, after impregnation, the vacuum degree of vacuum drying is -0.08 ~ -0.03 MPa, the drying time is 3-10 h, the temperature starts from 65-75 °C, and the heating rate is 0.3-0.7 °C / min.

[0048] The coating contains a micron-sized pore structure guided by cellulose acetate. During simple static impregnation, the amine functional monomers are easily limited by the concentration gradient, resulting in a slow diffusion rate and potentially insufficient adsorption deep within the pores. Oscillation, through mechanical disturbance, induces convection in the treatment solution, breaking the diffusion boundary layer and promoting the penetration of monomer molecules into the coating's internal pores. This is particularly beneficial for the complex pore structure of ceramic honeycomb substrates, shortening the time to reach adsorption equilibrium.

[0049] The oscillation continuously refreshes the monomer concentration on the coating surface with the treatment solution, ensuring full contact between the inner surface of the pores and the treatment solution, and achieving a uniform distribution of amine sites in the three-dimensional space of the coating.

[0050] Preferably, after impregnation, the vacuum degree of vacuum drying is -0.08 ~ -0.05 MPa, the drying time is 5-10 h, the temperature starts from 67-72℃, and the heating rate is 0.4-0.6℃ / min.

[0051] Secondly, the present invention provides an unsaturated metal-amine coordination polymer carbon filler, which is prepared by the aforementioned preparation method.

[0052] Thirdly, the present invention provides the application of the unsaturated metal-amine coordination polymer carbon fixative filler as a carbon dioxide adsorbent.

[0053] The present invention will be further described below with reference to the embodiments.

[0054] Example 1 A method for preparing an unsaturated metal-amine coordination polymer carbon filler includes the following steps: 1) Add 1 g of styrene-butadiene-styrene block copolymer (SBS) as the polymer matrix component to 10 ml of toluene, and swell in a sealed water bath at 40°C for 12 hours to form a homogeneous polymer mother liquor.

[0055] Subsequently, MIL-100(Cr) metal coordination polymer microcrystalline powder and cellulose acetate were added to the mother liquor in batches as pore structure guiding agents. The mass ratio of polymer matrix to metal coordination polymer was 2:1. The mixture was dispersed using an ultrasonic disperser for 30 minutes to achieve uniform fusion of polymer matrix and functional filler, thus obtaining a composite functional slurry with thixotropic properties.

[0056] 2) The obtained composite functional slurry was uniformly coated onto the surface of the pretreated ceramic honeycomb filler substrate using a scraping method, with an average coating thickness controlled at 350 μm. The coated sample was placed in a gradient temperature oven and treated at 50℃, 60℃, and 70℃ for 10 minutes each to allow the coating to gradually solidify and form an initial network structure. Subsequently, it was transferred to a vacuum drying oven and deeply dried at 70℃ and -0.08 MPa vacuum for 8 hours to remove residual solvents and allow polymer chain segments to rearrange to form a stable three-dimensional network structure, thus obtaining the intermediate.

[0057] 3) Dissolve 0.5 g of hydroxyethyl ethylenediamine in 50 mL of methanol and stir at 500 rpm for 10 minutes using a magnetic stirrer to obtain the amine functionalized grafting solution.

[0058] The intermediate prepared in step 2) was immersed in the amine functionalization grafting solution and placed in a constant temperature shaking incubator. It was treated for 3 hours at 25°C and 100 rpm to allow the amine functional monomer to fully diffuse and adsorb onto the inner surface of the coating pores.

[0059] After impregnation, the sample is removed and transferred to a vacuum drying oven. The heating rate is set at 0.5℃ / min, gradually increasing from room temperature to 70℃, while maintaining a vacuum of -0.08 MPa for 8 hours. Slow heating ensures stable solvent evaporation and avoids stress damage to the pore structure caused by rapid evaporation, thus obtaining an amine-functionalized monolithic adsorption packing.

[0060] Example 2 1) Add 0.5 g of styrene-butadiene-styrene block copolymer (SBS) as a polymer matrix component to 10 ml of toluene, and swell in a sealed water bath at 40 °C for 12 hours to form a homogeneous polymer mother liquor.

[0061] Subsequently, MIL-100(Cr) metal coordination polymer microcrystalline powder and cellulose acetate were added to the mother liquor in batches as pore structure guiding agents. The mass ratio of polymer matrix to metal coordination polymer was 1:1. The mixture was dispersed using an ultrasonic disperser for 30 minutes to achieve uniform fusion of polymer matrix and functional filler, thus obtaining a composite functional slurry with thixotropic properties.

[0062] 2) The obtained composite functional slurry was uniformly coated onto the surface of the pretreated ceramic honeycomb filler substrate using a scraping method, with an average coating thickness controlled at 350 μm. The coated sample was placed in a gradient temperature oven and treated at 50℃, 60℃, and 70℃ for 10 minutes each to allow the coating to gradually solidify and form an initial network structure. Subsequently, it was transferred to a vacuum drying oven and deeply dried at 70℃ and -0.08 MPa vacuum for 8 hours to remove residual solvents and allow polymer chain segments to rearrange to form a stable three-dimensional network structure, thus obtaining the intermediate.

[0063] 3) Dissolve 0.5g of hydroxyethyl ethylenediamine in 50 mL of methanol and stir at 500 rpm for 10 minutes using a magnetic stirrer to obtain the amine-functionalized grafting solution.

[0064] The intermediate prepared in step 2) was immersed in the amine functionalization grafting solution and placed in a constant temperature shaking incubator. It was treated for 3 hours at 25°C and 100 rpm to allow the amine functional monomer to fully diffuse and adsorb onto the inner surface of the coating pores.

[0065] After impregnation, remove the product and transfer it to a vacuum drying oven. Set the heating rate to 0.5℃ / min and gradually increase the temperature from room temperature to 70℃. Maintain the vacuum at -0.08 MPa and dry for 8 hours.

[0066] Example 3 1) Add 0.5 g of styrene-butadiene-styrene block copolymer (SBS) as a polymer matrix component to 10 ml of toluene, and swell in a sealed water bath at 40 °C for 12 hours to form a homogeneous polymer mother liquor.

[0067] Subsequently, MIL-100(Cr) metal coordination polymer microcrystalline powder and cellulose acetate were added to the mother liquor in batches as pore structure guiding agents. The mass ratio of polymer matrix to metal coordination polymer was 1:2. The mixture was dispersed using an ultrasonic disperser for 30 minutes to achieve uniform fusion of polymer matrix and functional filler, thus obtaining a composite functional slurry with thixotropic properties.

[0068] 2) The obtained composite functional slurry was uniformly coated onto the surface of the pretreated ceramic honeycomb filler substrate using a scraping method, with an average coating thickness controlled at 350 μm. The coated sample was placed in a gradient temperature oven and treated at 50℃, 60℃, and 70℃ for 10 minutes each to allow the coating to gradually solidify and form an initial network structure. Subsequently, it was transferred to a vacuum drying oven and deeply dried at 70℃ and -0.08 MPa vacuum for 8 hours to remove residual solvents and allow polymer chain segments to rearrange to form a stable three-dimensional network structure, thus obtaining the intermediate.

[0069] 3) Dissolve 0.5 g of hydroxyethyl ethylenediamine in 50 mL of methanol and stir with a magnetic stirrer at 500 rpm for 10 minutes to obtain the amine-functionalized grafting solution.

[0070] The intermediate prepared in step 2) was immersed in the amine functionalization grafting solution and placed in a constant temperature shaking incubator. It was treated for 3 hours at 25°C and 100 rpm to allow the amine functional monomer to fully diffuse and adsorb onto the inner surface of the coating pores.

[0071] After impregnation, remove the product and transfer it to a vacuum drying oven. Set the heating rate to 0.5℃ / min and gradually increase the temperature from room temperature to 70℃. Maintain the vacuum at -0.08 MPa and dry for 8 hours.

[0072] Example 4 1) Add 0.5 g of styrene-butadiene-styrene block copolymer (SBS) as a polymer matrix component to 10 ml of toluene, and swell in a sealed water bath at 40 °C for 12 hours to form a homogeneous polymer mother liquor.

[0073] Subsequently, MIL-100(Fe) metal coordination polymer microcrystalline powder and cellulose acetate were added to the mother liquor in batches as pore structure guiding agents. The mass ratio of polymer matrix to metal coordination polymer was 1:1. The mixture was dispersed using an ultrasonic disperser for 30 minutes to achieve uniform fusion of polymer matrix and functional filler, thus obtaining a composite functional slurry with thixotropic properties.

[0074] 2) The obtained composite functional slurry was uniformly coated onto the surface of the pretreated ceramic honeycomb filler substrate using a scraping method, with an average coating thickness controlled at 350 μm. The coated sample was placed in a gradient temperature oven and treated at 50℃, 60℃, and 70℃ for 10 minutes each to allow the coating to gradually solidify and form an initial network structure. Subsequently, it was transferred to a vacuum drying oven and deeply dried at 70℃ and -0.08 MPa vacuum for 8 hours to remove residual solvents and allow polymer chain segments to rearrange to form a stable three-dimensional network structure, thus obtaining the intermediate.

[0075] 3) Dissolve 0.5 g of hydroxyethyl ethylenediamine in 50 mL of methanol and stir with a magnetic stirrer at 500 rpm for 10 minutes to obtain the amine-functionalized grafting solution.

[0076] The intermediate prepared in step 2) was immersed in the amine functionalization grafting solution and placed in a constant temperature shaking incubator. It was treated for 3 hours at 25°C and 100 rpm to allow the amine functional monomer to fully diffuse and adsorb onto the inner surface of the coating pores.

[0077] After impregnation, remove the product and transfer it to a vacuum drying oven. Set the heating rate to 0.5℃ / min and gradually increase the temperature from room temperature to 70℃. Maintain the vacuum at -0.08 MPa and dry for 8 hours.

[0078] Example 5 1) Add 0.5g of styrene-butadiene-styrene block copolymer (SBS) as a polymer matrix component to 10ml of toluene, and swell in a sealed water bath at 40℃ for 12 hours to form a homogeneous polymer mother liquor.

[0079] Subsequently, UiO-66(Cr) metal coordination polymer microcrystalline powder and cellulose acetate were added to the mother liquor in batches as pore structure guiding agents. The mass ratio of polymer matrix to metal coordination polymer was 1:1. The mixture was dispersed using an ultrasonic disperser for 30 minutes to achieve uniform fusion of polymer matrix and functional filler, thus obtaining a composite functional slurry with thixotropic properties.

[0080] 2) The obtained composite functional slurry was uniformly coated onto the surface of the pretreated ceramic honeycomb filler substrate using a scraping method, with an average coating thickness controlled at 350 μm. The coated sample was placed in a gradient temperature oven and treated at 50℃, 60℃, and 70℃ for 10 minutes each to allow the coating to gradually solidify and form an initial network structure. Subsequently, it was transferred to a vacuum drying oven and deeply dried at 70℃ and -0.08 MPa vacuum for 8 hours to remove residual solvents and allow polymer chain segments to rearrange to form a stable three-dimensional network structure, thus obtaining the intermediate.

[0081] 3) Dissolve 0.5 g of hydroxyethyl ethylenediamine in 50 mL of methanol and stir with a magnetic stirrer at 500 rpm for 10 minutes to obtain the amine-functionalized grafting solution.

[0082] The intermediate prepared in step 2) was immersed in the amine functionalization grafting solution and placed in a constant temperature shaking incubator. It was treated for 3 hours at 25°C and 100 rpm to allow the amine functional monomer to fully diffuse and adsorb onto the inner surface of the coating pores.

[0083] After impregnation, remove the product and transfer it to a vacuum drying oven. Set the heating rate to 0.5℃ / min and gradually increase the temperature from room temperature to 70℃. Maintain the vacuum at -0.08 MPa and dry for 8 hours.

[0084] Example 6 1) Add 0.5 g of styrene-isoprene-styrene block copolymer (SIS) as a polymer matrix component to 10 ml of toluene, and swell in a sealed water bath at 40°C for 12 hours to form a homogeneous polymer mother liquor.

[0085] Subsequently, MIL-100(Cr) metal coordination polymer microcrystalline powder and cellulose acetate were added to the mother liquor in batches as pore structure guiding agents. The mass ratio of polymer matrix to metal coordination polymer was 1:1. The mixture was dispersed using an ultrasonic disperser for 30 minutes to achieve uniform fusion of polymer matrix and functional filler, thus obtaining a composite functional slurry with thixotropic properties.

[0086] 2) The obtained composite functional slurry was uniformly coated onto the surface of the pretreated ceramic honeycomb filler substrate using a scraping method, with an average coating thickness controlled at 350 μm. The coated sample was placed in a gradient temperature oven and treated at 50℃, 60℃, and 70℃ for 10 minutes each to allow the coating to gradually solidify and form an initial network structure. Subsequently, it was transferred to a vacuum drying oven and deeply dried at 70℃ and -0.08 MPa vacuum for 8 hours to remove residual solvents and allow polymer chain segments to rearrange to form a stable three-dimensional network structure, thus obtaining the intermediate.

[0087] 3) Dissolve 0.5 g of hydroxyethyl ethylenediamine in 50 mL of methanol and stir with a magnetic stirrer at 500 rpm for 10 minutes to obtain the amine-functionalized grafting solution.

[0088] The intermediate prepared in step 2) was immersed in the amine functionalization grafting solution and placed in a constant temperature shaking incubator. It was treated for 3 hours at 25°C and 100 rpm to allow the amine functional monomer to fully diffuse and adsorb onto the inner surface of the coating pores.

[0089] After impregnation, remove the product and transfer it to a vacuum drying oven. Set the heating rate to 0.5℃ / min and gradually increase the temperature from room temperature to 70℃. Maintain the vacuum at -0.08 MPa and dry for 8 hours.

[0090] Comparative Example 1 1) Add 0.5 g of styrene-butadiene-styrene block copolymer (SBS) as a polymer matrix component to 10 ml of toluene, and swell in a sealed water bath at 40 °C for 12 hours to form a homogeneous polymer mother liquor.

[0091] Subsequently, MIL-100(Cr) metal coordination polymer microcrystalline powder and cellulose acetate were added to the mother liquor in batches as pore structure guiding agents. The mass ratio of polymer matrix to metal coordination polymer was 1:1. The mixture was dispersed using an ultrasonic disperser for 30 minutes to achieve uniform fusion of polymer matrix and functional filler, thus obtaining a composite functional slurry with thixotropic properties.

[0092] 2) The obtained composite functional slurry was uniformly coated onto the surface of the pretreated ceramic honeycomb filler substrate using a scraping method, with an average coating thickness controlled at 350 μm. The coated sample was placed in a gradient temperature oven and treated at 50℃, 60℃, and 70℃ for 10 minutes each to allow the coating to gradually solidify and form an initial network structure. Subsequently, it was transferred to a vacuum drying oven and deeply dried at 70℃ and -0.08 MPa vacuum for 8 hours to remove residual solvents and allow polymer chain segments to rearrange to form a stable three-dimensional network structure, thus obtaining the intermediate.

[0093] 3) Dissolve 0.5 g of diethanolamine in 50 mL of methanol and stir with a magnetic stirrer at 500 rpm for 10 minutes to obtain the amine functionalized grafting solution.

[0094] The intermediate prepared in step 2) was immersed in the amine functionalization grafting solution and placed in a constant temperature shaking incubator. It was treated for 3 hours at 25°C and 100 rpm to allow the amine functional monomer to fully diffuse and adsorb onto the inner surface of the coating pores.

[0095] After impregnation, remove the product and transfer it to a vacuum drying oven. Set the heating rate to 0.5℃ / min and gradually increase the temperature from room temperature to 70℃. Maintain the vacuum at -0.08 MPa and dry for 8 hours.

[0096] Comparative Example 2 The difference from Example 2 is that step 3 is omitted, while everything else is the same as Example 2.

[0097] Comparative Example 3 The difference from Example 2 is that in step 2), "treat at 50℃, 60℃ and 70℃ for 10 minutes each" is replaced with "treat at 60℃ for 30 minutes", and everything else is the same as in Example 2.

[0098] Comparative Example 4 The difference from Example 2 is that in step 2), "treat at 50℃, 60℃ and 70℃ for 10 minutes each" is replaced with "treat at 70℃ for 30 minutes", and everything else is the same as in Example 2.

[0099] Comparative Example 5 The difference from Example 2 is that in step 2), "deep drying at 70°C and -0.08 MPa vacuum for 8 hours" is replaced with "deep drying at 100°C for 8 hours", and everything else is the same as in Example 2.

[0100] Comparative Example 6 The difference from Example 2 is that the oscillation operation is omitted in step 3), while everything else is the same as in Example 2.

[0101] Performance testing The fillers prepared in the examples and comparative examples were subjected to performance tests, and the test results are shown in Table 1.

[0102] Adsorption performance test method: A fixed-bed reactor was used, and a CO2 / N2 mixture with a CO2 concentration of 0.04% was introduced. The CO2 concentration in the reaction chamber was monitored in real time by infrared, and the adsorption capacity was calculated based on the amount of CO2 concentration reduction. Mechanical stability test method: The ultrasonic oscillation method is adopted. The filler material is placed in an ultrasonic bath at 25℃ and oscillated for 1 hour. The ultrasonic power is 500 W. The mechanical stability is evaluated by the mass loss rate before and after the test. The method for testing the cyclic stability of the packing material is as follows: After adsorption is complete, the reaction chamber is purged with moist nitrogen for 30 minutes. Then, the fixed-bed reactor is heated to 70°C and purged for another hour for regeneration. After the temperature drops to room temperature, a CO2 / N2 mixture with a concentration of 0.04% CO2 is introduced for the next round of adsorption experiments. The above operation is repeated to examine the cyclic stability of the packing material.

[0103] Table 1

[0104] Figure 1 The image shows the surface morphology of the metal-amine coordination polymer solid carbon filler (Example 2). The block structure of SBS imparts excellent elasticity, and the dense and compact surface of the material is beneficial for improving mechanical properties. Simultaneously, the presence of numerous wrinkles on the surface effectively disperses tensile stress, further enhancing the mechanical stability of the material.

[0105] Figure 2 Surface elemental analysis diagram of the metal-amine coordination polymer carbon filler (Example 2). EDS spectroscopy shows that N and O elements are uniformly distributed in the material, indicating that the amine functional groups are uniformly dispersed in the polymer matrix.

[0106] Figure 3 The graphs show the adsorption performance at different ratios of polymer matrix to metal coordination polymer. In Examples 1 to 3, the ratios of polymer matrix to metal coordination polymer were 2:1, 1:1, and 1:2, respectively. In Examples 1 and 2, the coatings remained intact without peeling, with adsorption capacities of 0.21 mmol / g and 0.45 mmol / g, respectively. In Example 3, microcracks appeared on the coating surface, and the adsorption capacity was 0.5 mmol / g. The results indicate that the adsorption performance improves with increasing metal coordination polymer ratio, but excessively high ratios lead to surface cracks and decreased mechanical properties.

[0107] Figure 4 The graph shows the adsorption performance of different types of metal coordination polymers. Examples 2, 4, and 5 used MIL-100 (Cr), MIL-100 (Fe), and UiO-66 (Zr) as metal coordination polymers, respectively. All three coatings remained intact without peeling, and their adsorption capacities were 0.45 mmol / g, 0.21 mmol / g, and 0.33 mmol / g, respectively. The results indicate that the type of metal ion has a significant impact on the adsorption performance. Cr-based MOFs exhibited the best adsorption capacity, which is attributed to the Cr... 3+ It possesses strong Lewis acidity and stability in coordination with amine groups, which is beneficial for forming more efficient amine-anchored structures.

[0108] Figure 5 The diagram shows the cyclic stability of the metal-amine coordination polymer carbon fixative packing material (Example 2). After 5 adsorption-desorption cycles, the adsorption capacity remained at approximately 0.4 mmol / g, indicating that the prepared packing material has excellent cyclic stability.

[0109] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an unsaturated metal-amine coordination polymer carbon filler, characterized in that: Includes the following steps: After the polymer mother liquor, unsaturated metal coordination polymer microcrystalline powder and cellulose acetate are mixed evenly in a certain proportion, a slurry is obtained. The polymer is an elastic polymer material. The slurry is uniformly coated on the surface of the filler substrate, first dried by gradient heating, and then dried in vacuum to allow the polymer chain segments to rearrange and form a three-dimensional network structure, thus obtaining the intermediate. The intermediate is immersed in an amine functionalization grafting solution, which allows the amine functional monomers in the amine functionalization grafting solution to diffuse and adsorb onto the inner surface of the coating pores. After impregnation, it is vacuum dried, with the temperature gradually increased during the drying process.

2. The method for preparing the unsaturated metal-amine coordination polymer carbon filler according to claim 1, characterized in that: The polymer matrix in the polymer mother liquor is a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, or a polyisobutylene-styrene block copolymer. Preferably, the polymer matrix is ​​a styrene-isoprene-styrene block copolymer; Preferably, the metal coordination polymer microcrystalline powder is selected from MIL-100 (Cr), UiO-66 (Zr) or MIL-100 (Fe) microcrystalline powder, and more preferably from MIL-100 (Cr) or UiO-66 (Zr) microcrystalline powder. Preferably, the mass ratio of the polymer matrix, the metal coordination polymer microcrystalline powder, and cellulose acetate is 1-3:1-3:1; Preferably, the mass ratio of the polymer matrix to the metal-coordinated polymer microcrystalline powder is 1-3:1-2, more preferably 1-3:1, and even more preferably 1:

1.

3. The method for preparing the unsaturated metal-amine coordination polymer carbon filler according to claim 1, characterized in that: The solvent in the polymer mother liquor is toluene, petroleum ether, or ethyl acetate; Preferably, the polymer mother liquor is prepared by adding the polymer matrix components to a solvent and swelling them in a sealed water bath at a constant temperature to form a homogeneous polymer mother liquor.

4. The method for preparing the unsaturated metal-amine coordination polymer carbon filler according to claim 1, characterized in that: The polymer mother liquor, metal coordination polymer microcrystalline powder and cellulose acetate were mixed in proportion and then ultrasonically dispersed to obtain a slurry. Alternatively, the filler substrate may be a ceramic honeycomb or corrugated ceramic. Preferably, after the slurry is uniformly applied to the surface of the filler substrate, the resulting coating thickness is 200-500 μm.

5. The method for preparing the unsaturated metal-amine coordination polymer carbon filler according to claim 1, characterized in that: The gradient temperature drying method involves drying at 45-53℃, 57-63℃, and 67-72℃ for 5-15 minutes sequentially. Alternatively, the temperature for vacuum deep drying is 65-75℃, the vacuum degree is -0.08 ~ -0.03MPa, and the drying time is 3-10h; Preferably, the temperature for vacuum deep drying is 67-72℃, the vacuum degree is -0.08 ~ -0.05MPa, and the drying time is 5-10h.

6. The method for preparing the unsaturated metal-amine coordination polymer carbon filler according to claim 1, characterized in that: The amine functional monomer in the amine-functionalized grafting solution is hydroxyethyl ethylenediamine, monoethanolamine, or diethanolamine. Preferably, the amino functional monomer is hydroxyethyl ethylenediamine; Preferably, the solvent in the amine functionalization grafting solution is an alcohol solvent.

7. The method for preparing the unsaturated metal-amine coordination polymer carbon filler according to claim 1, characterized in that: During the impregnation of the intermediate in the amine functionalization grafting solution, the impregnation was carried out by shaking at 80-120 rpm, 20-30℃, for 2-4 hours.

8. The method for preparing the unsaturated metal-amine coordination polymer carbon filler according to claim 1, characterized in that: After impregnation, the vacuum degree of vacuum drying is -0.08 ~ -0.03MPa, the drying time is 3-10h, the temperature starts from 65-75℃, and the heating rate is 0.3-0.7℃ / min; Preferably, after impregnation, the vacuum degree of vacuum drying is -0.08 ~ -0.05 MPa, the drying time is 5-10 h, the temperature starts from 67-72℃, and the heating rate is 0.4-0.6℃ / min.

9. An unsaturated metal-amine coordination polymer carbon fixative filler, characterized in that: It is prepared by any one of the preparation methods described in claims 1-8.

10. The use of the unsaturated metal-amine coordination polymer carbon filler of claim 9 as a carbon dioxide adsorbent.

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