Membrane-like carbon dioxide adsorbent and preparation method thereof

Abstract

The invention discloses a membranous carbon dioxide adsorbent and a preparation method thereof. The membrane-like carbon dioxide is prepared on the basis of chlorine-containing waste plastics, the adsorbent is stable in performance, the preparation process is mild and economical, and the membrane-like carbon dioxide has extremely high industrial popularization value.

Description

Technical Field

[0001] This invention belongs to the field of carbon capture materials technology, specifically, it relates to a membrane-like carbon dioxide adsorbent and its preparation method. Background Technology

[0002] With the intensifying challenges of global climate change, carbon dioxide capture, storage, and utilization (CCUS) has become a key technological aspect, with direct air capture (DAC) technology attracting significant attention due to its potential to remove historical carbon emissions from the atmosphere. On the other hand, chlorine-containing wastes, such as polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC), are widely used (e.g., in building pipes and medical consumables) but are difficult to degrade, thus posing a challenge to solid waste management. Converting these waste plastics into high-performance carbon capture materials could potentially achieve both environmental and economic benefits. However, despite some progress in related research, existing preparation technologies still face numerous substantial challenges in moving chlorine-containing plastic-based adsorbent materials from the laboratory to large-scale applications.

[0003] Currently, the mainstream processes for modifying or carbonizing waste chlorinated plastics mostly rely on high-temperature, high-pressure hydrothermal reactor systems. These methods often require long-term reactions at temperatures of 120–180°C or even higher and pressures exceeding 1 MPa. These harsh conditions not only result in extremely high energy consumption but also impose stringent requirements on the pressure resistance and corrosion resistance of the reactor, thus raising the investment threshold and safety requirements for equipment, which contradicts the original intention of low-carbon and environmentally friendly practices. At the material structure level, the inherent flexible polymer chain characteristics of chlorinated plastics also pose obstacles to the preparation of high-performance adsorbents. Although the polymer chains are stretched in the solvent, during the subsequent drying and solvent removal process, driven by huge capillary contraction forces, the lack of rigid support in the skeleton easily leads to irreversible shrinkage and collapse. This "pore collapse" effect directly results in the closure of micropores and a significant loss of specific surface area in the final material, severely limiting the material's physical adsorption potential for gas molecules and the subsequent loading capacity of active sites.

[0004] Existing modification strategies still fall short in addressing the cycling stability and adsorption kinetics of adsorbents. While traditional physical impregnation methods are simple to operate, the lack of strong chemical bonds between the amine component and the framework leads to the easy volatilization or loss of amine molecules during temperature-controlled or vacuum desorption cycles, resulting in a sharp decline in adsorption performance with increasing usage. Simultaneously, simple physical coating often causes pore blockage, increasing the internal diffusion resistance of gas molecules and making it difficult to meet the rapid cycling requirements of industrial applications. More critically, existing technologies often produce products in powder or irregular particle form, inevitably leading to engineering challenges such as high packing density, high bed pressure drop, and susceptibility to airflow channeling in practical industrial applications, especially in high-volume direct air capture (DAC) scenarios. Furthermore, while most traditional adsorbents may perform reasonably well when treating high-concentration CO2 flue gas, they often exhibit extremely limited adsorption capacity when facing extremely low partial pressures (460 ppm) of CO2 in the atmosphere due to insufficient dispersion of active sites or a lack of effective micropore confinement enhancement effects, failing to meet the stringent high-performance requirements of direct air capture.

[0005] Based on the above situation, developing a carbon dioxide adsorbent based on chlorine-containing waste plastics that has a mild process, stable structure, resistance to amine loss, and excellent adsorption kinetics and high capacity under low carbon dioxide partial pressure has become the focus of breaking through the bottleneck of existing technology. Summary of the Invention

[0006] To address the problems of low recycling rate of chlorine-containing waste plastics, high energy consumption in the preparation of traditional adsorbents, and poor cycle stability in existing technologies, this invention provides a stable, mild, and economical membrane carbon dioxide adsorbent based on chlorine-containing waste plastics and its preparation method.

[0007] In one aspect, the present invention provides a method for preparing a membrane-like carbon dioxide adsorbent, the method comprising the following steps:

[0008] S1. Dissolution: Add the crushed chlorine-containing plastic to an organic solvent, heat to 55-65℃, and stir to completely dissolve the chlorine-containing plastic to obtain a waste plastic dispersion.

[0009] S2, Crosslinking: Add a rigid crosslinking agent to the waste plastic dispersion, stir and age at 60-70℃ for 1-2 h to obtain a crosslinked plastic solution;

[0010] S3. Preparation of precursor solution: Add catalyst to crosslinked plastic solution and heat under reflux at 60-80℃ for 0.5-1 h to obtain precursor solution;

[0011] S4. Amination: Add an amination reagent to the precursor solution and heat under reflux at 55-65°C for 2-4 hours to obtain an amination plastic solution.

[0012] S5. Loading: Immerse the substrate material in the aminated plastic solution for 10–30 min;

[0013] S6. Drying: After the loading is completed, the substrate material loaded with amination plastic is taken out, immersed in phase separation reagent for 0.1 to 1 h, and then vacuum dried at 50 to 80 °C to obtain the membrane carbon dioxide adsorbent.

[0014] Preferably, the particle size of the pulverized chlorine-containing plastic is 60-100 mesh.

[0015] In one or more embodiments, the chlorinated plastic is polyvinyl chloride, and the organic solvent is a polar aprotic solvent; the mass ratio of the chlorinated plastic to the volume of the organic solvent is 1 g:(5-100) mL.

[0016] Preferably, the polar aprotic solvent is selected from at least one of dimethyl sulfoxide, hexamethylphosphoric triamine, N-methyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, cyclohexanone, and acetonitrile. More preferably, the polar aprotic solvent is N,N-dimethylformamide.

[0017] Preferably, the ratio of the mass of the chlorinated plastic to the volume of the organic solvent is 1 g:(10-30) mL.

[0018] In one or more embodiments, the rigid crosslinking agent is selected from at least one of biphenyl, terphenyl, naphthalene, anthracene, triterpenes, p-dichlorobenzyl, p-phenylenediamine, melamine, chlorotrihydrogen phosphate, 4,4'-diaminodiphenylmethane, triterpenes, spirodifluorene, tetraphenylmethane, 1,3,5-triphenylbenzene, and hexamethylenetetramine; the mass ratio of the rigid crosslinking agent to the chlorinated plastic is 0.1 to 1.5.

[0019] Preferably, the rigid crosslinking agent is biphenyl.

[0020] Preferably, the mass ratio of the rigid crosslinking agent to the chlorine-containing plastic is 0.2 to 0.8.

[0021] In one or more embodiments, the catalyst is at least one of a Lewis acid catalyst and a phase transfer catalyst; the Lewis acid catalyst is selected from at least one of zinc chloride, ferric chloride, aluminum chloride, tin chloride, titanium chloride, copper chloride, cobalt chloride, nickel chloride, antimony trichloride, antimony pentachloride, and boron trifluoride diethyl ether; the phase transfer catalyst is selected from at least one of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, tetraoctylammonium bromide, tetrabutylphosphine bromide, tetraphenylphosphine bromide, polyethylene glycol-400, and polyethylene glycol-600; the mass ratio of the catalyst to the chlorine-containing plastic is 0.05 to 1.

[0022] Preferably, the Lewis acid catalyst is zinc chloride.

[0023] Preferably, the mass ratio of the catalyst to the chlorinated plastic is 0.1 to 0.5.

[0024] In one or more embodiments, the amination agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, tris(2-aminoethyl)amine, and polyacrylamine; the mass ratio of the amination agent to the chlorinated plastic is 0.2 to 5.

[0025] Preferably, the amination reagent is tetraethylenepentamine or polyethyleneimine.

[0026] Preferably, the mass ratio of the amination reagent to the chlorine-containing plastic is 0.8 to 1.5.

[0027] In one or more embodiments, the substrate material is selected from at least one of porous carbon materials, inorganic oxides or silicate materials, and structured framework materials; the porous carbon material is selected from at least one of activated carbon powder, activated carbon fiber, carbon nanotubes, graphene, graphene oxide, and biochar; the inorganic oxides or silicate materials include at least one of mesoporous silica, fumed silica, silica gel, alumina, zeolite molecular sieves, diatomaceous earth, bentonite, and kaolin; and the structured framework material is selected from at least one of glass fiber, ceramic honeycomb, foamed metal, and stainless steel mesh.

[0028] In one or more embodiments, the phase separation reagent is water, ethanol, or a mixture of both.

[0029] In another aspect, the present invention provides a membrane-like carbon dioxide adsorbent prepared by means of the method described in any embodiment herein.

[0030] In another aspect, the present invention provides the application of membrane-like carbon dioxide adsorbents as described in any embodiment herein in carbon dioxide capture.

[0031] This invention follows the concept of "treating waste with waste and high-value conversion," utilizing chemical modification to transform recalcitrant chlorine-containing waste plastics into highly efficient carbon capture materials. Compared to traditional physical adsorption materials (such as zeolite and activated carbon), this invention introduces a rigid crosslinking agent to construct a stable microstructure, effectively solving the problem of polymer channel collapse. Furthermore, it uses chemical grafting technology to anchor a high density of amine active sites on the framework, thereby endowing the material with CO2 capture capacity and selectivity far superior to physical adsorption materials under low partial pressures (such as in direct air capture processes). Simultaneously, compared to traditional amine liquid absorption or physically impregnated adsorbents, the chemically bonded structure of this invention significantly improves the material's water resistance and resistance to amine loss, exhibiting significant advantages such as low regeneration energy consumption, long cycle life, and low corrosivity. It has broad application prospects in industrial flue gas treatment and direct air capture.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] 1. This invention employs a polar aprotic solvent reaction system, abandoning the harsh synthesis route of traditional techniques that rely on high-temperature and high-pressure hydrothermal reactors. Compared to the reaction temperature of 120–180°C and the reaction pressure of 1 MPa in a hydrothermal reactor, the preparation method of this invention can significantly reduce the reaction activation energy under mild conditions of atmospheric pressure and 60–80°C by utilizing the solvent effect, efficiently completing the chemical modification of chlorinated plastics. This significantly reduces the energy consumption and equipment threshold of preparation, successfully realizing the low-cost recycling and transformation of refractory chlorinated waste in the construction, medical and other fields. On the other hand, combined with the substrate loading process, it endows the flexible polymer with excellent mechanical support and membrane processing properties, effectively solving the pain points of large pressure drop and difficulty in molding of traditional powdered adsorbents in industrial applications, and has extremely high industrial promotion value.

[0034] 2. This invention introduces a rigid aromatic crosslinking agent into a homogeneous system and, in conjunction with a Lewis acid or phase transfer catalyst, induces an in-situ "hypercrosslinking" reaction between the polymer chains of flexible chlorinated plastics, successfully constructing a stable three-dimensional rigid network framework. This rigid framework plays a crucial "molecular pillar" role at the microscopic level, effectively resisting the huge capillary contraction forces generated during subsequent desolvation and drying processes, preventing the collapse of the porous structure, thereby endowing the adsorbent with a permanent microporous structure and a significantly increased specific surface area, greatly enhancing the material's physical capture potential energy and adsorption capacity for carbon dioxide molecules.

[0035] 3. This invention creatively utilizes the synergistic effect of highly active amination reaction and non-solvent-induced phase separation technology to achieve the simultaneous construction of "chemical functionalization" and "physical structuring" of the adsorbent. On the one hand, the amination reagent is stably grafted onto the plastic framework through strong CN covalent bonds, rather than simple physical attachment, fundamentally overcoming the bottleneck of performance degradation caused by the loss of amine components in traditional solid amine materials during regeneration cycles. On the other hand, the multi-level interconnected network of macropores, mesopores, and micropores induced during solvent replacement provides low-resistance diffusion channels for gas molecules, significantly eliminating internal diffusion limitations. As a result, the obtained material has both long-term cycling stability and extremely high carbon dioxide adsorption and desorption kinetic rates.

[0036] 4. This invention utilizes a rigid microporous framework to effectively disperse high-density amine sites and the "micropore confinement" effect, significantly enhancing the interaction potential energy between active sites and low-concentration carbon dioxide molecules. This allows the material to maintain an extremely high saturated adsorption capacity (up to 1.72 mmol / g) even at extremely low carbon dioxide partial pressures (460 ppm in the atmosphere), overcoming the technical shortcomings of traditional porous membrane materials that are severely limited under low pressure. This enables the efficient enrichment of carbon dioxide directly from the air, providing core material support for reducing the operating cost and energy consumption of DAC technology. Attached Figure Description

[0037] Figure 1 This is a flowchart of the preparation process for membrane adsorbents.

[0038] Figure 2 This is an observation diagram of the membrane adsorbent in Example 1.

[0039] Figure 3 This is a scanning electron microscope image of the membrane adsorbent of Example 1.

[0040] Figure 4 The N2 adsorption-desorption curves are for the membrane adsorbent of Example 1.

[0041] Figure 5 The image shows the static CO2 adsorption curve of the membrane adsorbent in Example 1.

[0042] Figure 6 The CO2 penetration curves of the membrane adsorbents in Examples 1-6 are shown.

[0043] Figure 7 The CO2 penetration curves of the membrane adsorbents in air for Example 1 and Comparative Examples 1-5 are shown. Detailed Implementation

[0044] Preferably, the preparation process of the membrane adsorbent of the present invention is as follows: Figure 1 As shown.

[0045] In the following examples or comparative examples, the specific test methods for each performance index of the membrane adsorbent are as follows:

[0046] Specific surface area and pore structure: The specific surface area and pore size were analyzed using a fully automated specific surface area and pore size analyzer (Micromeritics ASAP2020). Before analysis, the membrane adsorbent samples were degassed under N2 conditions at 100–120℃ for 6–12 hours to remove adsorbed moisture and impurity gases from the pores. Subsequently, the nitrogen adsorption-desorption isotherm of the membrane adsorbent was measured at liquid nitrogen temperature (77 K). Based on the BET (Brunauer-Emmett-Teller) equation, adsorption data with relative pressure P / P0 in the range of 0.05–0.3 were used to calculate the specific surface area of ​​the samples; the pore size distribution and total pore volume were calculated based on the BJH (Barrett-Joyner-Halenda) model and desorption branch data.

[0047] Static carbon dioxide adsorption capacity: The adsorption capacity was measured using a physical adsorption instrument in an ice-water bath environment (273 K). The membrane adsorbent sample was vacuum activated before testing. During the test, the CO2 pressure was gradually increased, and the equilibrium adsorption capacity at different pressures was recorded. Adsorption isotherms were plotted in the range of 0–100 kPa. The adsorption capacity at a CO2 pressure of 1 bar (100 kPa) was taken as the static saturated CO2 adsorption capacity of the material.

[0048] DAC dynamic breakthrough curve and adsorption kinetics: The test was conducted using a fixed-bed dynamic adsorption test apparatus. The specific operation was as follows: 0.5 g of the test membrane adsorbent sample was densely packed into a quartz adsorption column (inner diameter 18 mm); the adsorption column was kept at 25°C and activated by purging with high-purity N2; subsequently, simulated air (with N2 as the equilibrium gas, containing 460 ppm CO2) was introduced, the gas flow rate was set to 250 mL / min, and the pressure was atmospheric pressure; the change in CO2 concentration at the outlet was monitored in real time using an online infrared gas analyzer, and the breakthrough curve was plotted with time as the x-axis and CO2 outlet concentration as the y-axis.

[0049] Vacuum Desorption: After the adsorption stage is complete, close the inlet valve of the adsorption column to cut off the simulated air supply; then turn on the vacuum pump connected to the outlet of the adsorption column to evacuate the column. Control the system pressure to rapidly drop from atmospheric pressure to negative pressure within 2 minutes. Utilize the large pressure difference to break the chemical bonds formed between the amine groups and carbon dioxide on the surface of the membrane adsorbent (similar to the CN covalent bonds in amides), driving the adsorbate to rapidly desorb from the pores. Maintain this vacuum level and continue evacuation for 15 minutes until the vacuum gauge reading stabilizes and the desorption gas flow rate approaches zero, indicating complete desorption. Turn off the vacuum pump and slowly introduce dry air to restore the system pressure to atmospheric pressure, preparing for the next round of adsorption.

[0050] In the following examples or comparative examples, the gas breakthrough time was measured in a closed container containing an adsorbent. The breakthrough time was defined as the time from the start of the inlet input of a gas until the gas concentration at the outlet reaches 5% (C0) of the inlet gas concentration. out / C in = 0.05) The time required.

[0051] In the following examples or comparative examples, the half-adsorption saturation time is defined as the time it takes for the adsorbent to absorb a gas from zero to 50% of its dynamic saturation adsorption capacity. This indicator is used to measure the adsorption kinetic rate, and the shorter the half-adsorption saturation time, the faster the adsorption rate.

[0052] In the following embodiments or comparative examples, the desorption rate is calculated using the following formula:

[0053] ;

[0054] in The desorption rate; The saturated adsorption capacity during the adsorption phase is expressed in mmol / g. The actual desorption capacity during the desorption phase is expressed in mmol / g.

[0055] In the following embodiments or comparative examples, the formula for calculating the cycle retention rate is:

[0056] ;

[0057] in The retention rate for the nth cycle; The adsorption amount for the nth time is expressed in mmol / g. The adsorption amount for the first time is expressed in mmol / g.

[0058] In the following embodiments or comparative examples, the formula for calculating the dynamic adsorption amount of the DAC is as follows:

[0059] ;

[0060] in The dynamic saturated adsorption capacity is expressed in mmol / g. The flow rate of the feed gas is taken as 250 mL / min; To input the volume fraction of CO2 in the gas, take 460 × 10⁻⁶. -6 (460 ppm); This represents the volume fraction of CO2 in the output gas. The adsorbent loading mass is 0.5 g. The molar volume of the gas is taken as 22400 mL / mol under standard conditions; The time for adsorption saturation, i.e. The time is expressed in minutes.

[0061] Example 1

[0062] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N,N-dimethylformamide. Stir the mixture in a 60°C water bath with a magnetic stirrer at 400 rpm for approximately 30 minutes until completely dissolved, obtaining a homogeneous and transparent waste plastic dispersion. Add 1.5 g of the rigid crosslinking agent biphenyl to this dispersion, raise the system temperature to 65°C, and maintain the temperature with stirring for 1.5 hours. Add 1.0 g of anhydrous zinc chloride, a Lewis acid catalyst, to the solution, raise the temperature to 75°C, and reflux under nitrogen protection for 1 hour to obtain a dark brown porous polymerization precursor solution. Lower the reaction system temperature to 60°C and slowly add 5.0 g of biphenyl... After adding g of highly active amination reagent tetraethylenepentamine, the reaction was continued at 60°C under reflux for 3 hours to obtain an amination solution. A clean glass fiber cloth was used as a substrate and immersed in the above amination solution for 15 minutes. After removal, it was immediately immersed in a 1:1 volume ratio ethanol / water coagulation bath for 30 minutes. After complete solvent replacement, it was placed in a 60°C vacuum oven to dry for 12 hours to obtain the membrane carbon dioxide adsorbent with rigid skeleton support.

[0063] The prepared membrane adsorbent was observed directly and also observed using a scanning electron microscope (SEM). The observation results are as follows: Figure 2 and Figure 3 As shown. Combined with Figure 2 Macroscopic physical objects and Figure 3 As shown in the SEM images, the membrane adsorbent prepared in Example 1 appears as a uniform, intact, translucent, yellowish-brown flexible membrane. The polymer matrix is ​​uniformly impregnated and tightly adhered to the surface of the glass fiber cloth, with no obvious peeling or cracking macroscopically. The SEM images reveal a highly interconnected "sponge-like" network of mesopores and macropores on the material surface, accompanied by a clear fiber skeleton coating texture, induced by non-solvent-induced phase separation technology. This unique composite structure of "rigid fiber skeleton support - multi-level porous polymer filling" is beneficial for imparting excellent mechanical strength to the material while constructing low-resistance, high-speed diffusion channels for gas molecules. The membrane adsorbent was taken and measured as follows... Figure 4 The N2 adsorption-desorption curves are shown, and the specific surface area and pore structure are calculated based on them.

[0064] Take 50 mg of the membrane adsorbent and determine its static CO2 adsorption capacity at 0℃ and 1 bar atmospheric pressure. Figure 5As shown, the adsorption capacity of the material was measured to be 2.51 mmol / g, and the adsorption half-saturation time was 3.5 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low-partial-pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 16.8 min. Figure 6 The integral of the curve in Example 1 showed that the adsorption capacity was 1.72 mmol / g at a concentration of 460 ppm CO2. Vacuum desorption was then performed. The gas inlet was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 99.8%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 98.5%.

[0065] Example 2

[0066] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N-methyl-2-pyrrolidone. Stir the mixture in a 60°C water bath with magnetic stirring at 400 rpm until completely dissolved to obtain a homogeneous and transparent waste plastic dispersion. Add 2.0 g of the rigid crosslinking agent naphthalene to this dispersion, raise the system temperature to 70°C, and maintain the temperature with stirring for 2 hours. Add 1.5 g of anhydrous ferric chloride, a Lewis acid catalyst, to the solution, raise the temperature to 80°C, and reflux under nitrogen protection for 0.5 hours to obtain a dark-colored porous polymerization precursor solution. Lower the reaction system temperature to 60°C and slowly add 6.0 g of naphthalene... After adding g of highly active amination reagent polyethyleneimine (PEI), the reaction was continued at 60°C for 4 hours to obtain an amination solution. Clean activated carbon fiber was used as a substrate and immersed in the above amination solution for 20 minutes. After being removed, it was immediately immersed in water for 30 minutes. After complete solvent replacement, it was placed in a vacuum oven at 70°C and dried for 12 hours to obtain the membrane carbon dioxide adsorbent with rigid skeleton support.

[0067] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was measured at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 2.47 mmol / g, and the adsorption half-saturation time was 3.8 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low-partial-pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 15.9 min. Figure 6The integral of the curve in Example 2 showed that the adsorption capacity was 1.62 mmol / g at a concentration of 460 ppm CO2. Vacuum desorption was then performed. The air intake was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 99.6%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 98.2%.

[0068] Example 3

[0069] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of dimethyl sulfoxide. Stir until completely dissolved in a water bath at 60 °C and with magnetic stirring at 400 rpm to obtain a homogeneous and transparent waste plastic dispersion. Add 2.5 g of rigid crosslinking agent 1,3,5-triphenylbenzene to the dispersion, raise the system temperature to 70 °C, and maintain the temperature with stirring for 1 hour. Add 0.5 g of phase transfer catalyst tetrabutylammonium iodide to the solution, raise the temperature to 80 °C, and reflux under nitrogen protection for 1 hour to activate the reaction sites and promote crosslinking, obtaining a viscous polymerization precursor solution. Lower the reaction system temperature to 60 °C and slowly add 7.5 g of... After adding g of highly active amination reagent pentaethylenehexamine, the reaction was continued at 60°C under reflux for 3 hours to obtain an amination solution. A clean ceramic honeycomb was used as a substrate and immersed in the above amination solution for 10 minutes. After being removed, it was immediately immersed in ethanol for 30 minutes. After complete solvent replacement, it was placed in a vacuum oven at 80°C and dried for 10 hours to obtain the membrane carbon dioxide adsorbent with rigid skeleton support.

[0070] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was measured at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 2.39 mmol / g, and the adsorption half-saturation time was 4.2 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low partial pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 14.8 min. Figure 6 The integral of the curve in Example 3 showed that the adsorption capacity was 1.55 mmol / g at a concentration of 460 ppm CO2. Vacuum desorption was then performed. The air intake was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 99.5%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 97.9%.

[0071] Example 4

[0072] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N,N-dimethylacetamide. Stir the mixture in a 60°C water bath with magnetic stirring at 400 rpm until completely dissolved to obtain a homogeneous and transparent waste plastic dispersion. Add 1.0 g of nitrogen-containing rigid crosslinking agent melamine to the dispersion, raise the system temperature to 65°C, and maintain the temperature with stirring for 2 hours. Add 1.2 g of Lewis acid catalyst anhydrous aluminum trichloride to the solution, raise the temperature to 75°C, and reflux under nitrogen protection for 1 hour to obtain a dark-colored porous polymerization precursor solution. Lower the reaction system temperature to 60°C and slowly add 4.0 g of... After adding g of highly active amination reagent diethylenetriamine, the reaction was continued at 60°C under reflux for 4 hours to obtain an amination solution. A clean stainless steel mesh was used as a substrate and immersed in the above amination solution for 30 minutes. After being removed, it was immediately immersed in water for 30 minutes. After complete solvent replacement, it was placed in a vacuum oven at 60°C and dried for 12 hours to obtain the membrane carbon dioxide adsorbent with rigid skeleton support.

[0073] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was determined at 0℃ and 1 bar atmospheric pressure. The adsorption capacity was found to be 2.35 mmol / g, and the adsorption half-saturation time was 4 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low-partial-pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 14.9 min. Figure 6 The integral of the curve in Example 4 showed that the adsorption capacity was 1.52 mmol / g at a concentration of 460 ppm CO2. Vacuum desorption was then performed. The gas inlet was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 99.5%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 98.1%.

[0074] Example 5

[0075] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of cyclohexanone. Stir the mixture in a 60°C water bath with magnetic stirring at 400 rpm until completely dissolved to obtain a homogeneous and transparent waste plastic dispersion. Add 3.0 g of the rigid crosslinking agent p-dichlorobenzyl to this dispersion, raise the system temperature to 60°C, and maintain the temperature with stirring for 1 hour. Add 0.8 g of the Lewis acid catalyst tin tetrachloride to the solution, raise the temperature to 80°C, and reflux under nitrogen protection for 0.5 hours to obtain a porous polymerization precursor solution. Lower the reaction system temperature to 60°C and slowly add 5.0 g of cyclohexanone. After adding g of highly active amination reagent tris(2-aminoethyl)amine, the reaction was continued at 60°C under reflux for 2 hours to obtain an amination solution. A clean mesoporous silica sheet was used as a substrate and immersed in the above amination solution for 15 minutes. After removal, it was immediately immersed in a 1:1 volume ratio ethanol / water coagulation bath for 30 minutes. After complete solvent replacement, it was placed in a 50°C vacuum oven for 12 hours to dry, thus obtaining the membrane carbon dioxide adsorbent with rigid framework support.

[0076] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was measured at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 2.43 mmol / g, and the adsorption half-saturation time was 4.5 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low partial pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 13.9 min. Figure 6 The integral of the curve in Example 5 showed that the adsorption capacity was 1.42 mmol / g at a concentration of 460 ppm CO2. Vacuum desorption was then performed. The air intake was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 99.2%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 97.5%.

[0077] Example 6

[0078] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of tetrahydrofuran. Stir the mixture in a 60°C water bath with magnetic stirring at 400 rpm until completely dissolved to obtain a homogeneous and transparent waste plastic dispersion. Add 1.5 g of the stereocritical crosslinking agent triterene to the dispersion, raise the system temperature to 65°C, and maintain the temperature with stirring for 1.5 hours. Add 1.0 g of the Lewis acid catalyst boron trifluoride diethyl ether to the solution, raise the temperature to 65°C, and reflux under nitrogen protection for 1 hour to obtain a polymerization precursor solution. Lower the reaction system temperature to 60°C and slowly add 4.5 g of... After adding g of highly active amination reagent triethylenetetramine, the reaction was continued at 60°C under reflux for 3 hours to obtain an amination solution. Clean nickel foam was used as a substrate and immersed in the above amination solution for 20 minutes. After removal, it was immediately immersed in ethanol for 30 minutes. After complete solvent replacement, it was placed in a vacuum oven at 60°C and dried for 12 hours to obtain the membrane carbon dioxide adsorbent with rigid framework support.

[0079] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was measured at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 2.38 mmol / g, and the adsorption half-saturation time was 4.8 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low-partial-pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 4.8 min. Figure 6 The integral of the curve in Example 6 showed that the adsorption capacity was 1.36 mmol / g at a concentration of 460 ppm CO2. Vacuum desorption was then performed. The gas inlet was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 98.9%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 97.2%.

[0080] Comparative Example 1

[0081] The only difference between this comparative example and Example 1 is that the rigid crosslinking agent biphenyl is not added; all other steps and parameters are consistent with Example 1. The specific synthesis steps are as follows:

[0082] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N,N-dimethylformamide. Stir the mixture in a 60°C water bath with a magnetic stirrer at 400 rpm for approximately 30 minutes until completely dissolved, obtaining a homogeneous and transparent waste plastic dispersion. Raise the system temperature to 65°C and maintain the temperature with stirring for 1.5 hours. Add 1.0 g of anhydrous zinc chloride, a Lewis acid catalyst, to the solution, raise the temperature to 75°C, and reflux under nitrogen protection for 1 hour to obtain a dark brown porous polymerization precursor solution. Lower the reaction system temperature to 60°C and slowly add 5.0 g of... After adding g of highly active amination reagent tetraethylenepentamine, continue the reaction at 60°C for 3 hours to obtain an amination solution. Take a clean glass fiber cloth as a substrate and immerse it in the above amination solution for 15 minutes. After taking it out, immediately immerse it in a coagulation bath with a volume ratio of 1:1 ethanol / water for 30 minutes. After complete solvent replacement, place it in a vacuum oven at 60°C for 12 hours to dry.

[0083] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was measured at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 1.58 mmol / g, and the adsorption half-saturation time was 12.5 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low partial pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 9.2 min. Figure 7 The integral of the curve in Comparative Example 1 showed that the adsorption capacity was 0.95 mmol / g at a concentration of 460 ppm CO2. Vacuum desorption was then performed. The gas inlet was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 92.5%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 88.6%.

[0084] Comparative Example 2

[0085] The only difference between this comparative example and Example 1 is that after the substrate is soaked in the amination solution, it is not immersed in an ethanol / water mixed coagulation bath, but is directly vacuum dried. All other steps and parameters are consistent with Example 1. The specific synthesis steps are as follows:

[0086] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N,N-dimethylformamide. Stir for about 30 minutes under a 60°C water bath and 400 rpm magnetic stirring until completely dissolved to obtain a homogeneous and transparent waste plastic dispersion. Add 1.5 g of the rigid crosslinking agent biphenyl to the dispersion, raise the system temperature to 65°C, and maintain the temperature for stirring and aging for 1.5 hours. Add 1.0 g of Lewis acid catalyst anhydrous zinc chloride to the solution, raise the temperature to 75°C, and reflux under nitrogen protection for 1 hour to obtain a dark brown porous polymerization precursor solution. Lower the reaction system temperature to 60°C, and slowly add 5.0 g of the highly active amination reagent tetraethylenepentamine. After the addition is complete, continue to reflux at 60°C for 3 hours to obtain an amination solution. Take a clean glass fiber cloth as a substrate, immerse it in the above amination solution for 15 minutes, remove it, and dry it in a 60°C vacuum oven for 12 hours.

[0087] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was determined at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 0.91 mmol / g, and the adsorption half-saturation time was 25 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low-partial-pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 4.1 min. Figure 7 The integral of Comparative Example 2 showed that the adsorption capacity at a concentration of 460 ppm CO2 was 0.42 mmol / g. Subsequently, vacuum desorption was performed. The air intake was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 85.2%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 90.5%.

[0088] Comparative Example 3

[0089] The only difference between this comparative example and Example 1 is that the Lewis acid catalyst anhydrous zinc chloride is not added; all other steps and parameters are consistent with Example 1. The specific synthesis steps are as follows:

[0090] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N,N-dimethylformamide. Stir for about 30 minutes under a 60°C water bath and a magnetic stirrer at 400 rpm until completely dissolved to obtain a uniform and transparent waste plastic dispersion. Add 1.5 g of the rigid crosslinking agent biphenyl to the dispersion, raise the system temperature to 65°C, and maintain the temperature for stirring and aging for 1.5 hours. Slowly add 5.0 g of the highly active amination reagent tetraethylenepentamine. After the addition is complete, continue to reflux at 60°C for 3 hours to obtain an amination solution. Take a clean glass fiber cloth as a substrate and immerse it in the above amination solution for 15 minutes. After removing it, place it in a vacuum oven at 60°C and dry for 12 hours.

[0091] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was determined at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 0.71 mmol / g, and the adsorption half-saturation time was 8 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low partial pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 4.4 min. Figure 7 The integral of Comparative Example 3 showed that the adsorption capacity at a concentration of 460 ppm CO2 was 0.45 mmol / g. Subsequently, vacuum desorption was performed. The air intake was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 95.0%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 45.2%.

[0092] Comparative Example 4

[0093] The only difference between this comparative example and Example 1 is that the step of preparing the polymerization precursor is omitted, and the waste plastic dispersion and the amination reagent are only physically mixed to obtain the amination solution. All other steps and parameters are consistent with Example 1. The specific synthesis steps are as follows:

[0094] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N,N-dimethylformamide. Stir for about 30 minutes under a 60°C water bath and a magnetic stirrer at 400 rpm until completely dissolved to obtain a uniform and transparent waste plastic dispersion. Slowly add 5.0 g of the highly active amination reagent tetraethylenepentamine. After the addition is complete, continue to reflux at 60°C for 3 hours, and use mechanical stirring for physical mixing to obtain an amination solution. Take a clean glass fiber cloth as a substrate and immerse it in the above amination solution for 15 minutes. After removing it, place it in a vacuum oven at 60°C and dry for 12 hours.

[0095] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was determined at 0℃ and 1 bar atmospheric pressure. The adsorption capacity was found to be 0.58 mmol / g, and the adsorption half-saturation time was 6.5 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low-partial-pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 1.5 min. Figure 7 The integral of Comparative Example 4 showed that the adsorption capacity at a concentration of 460 ppm CO2 was 0.15 mmol / g. Subsequently, vacuum desorption was performed. The gas inlet was stopped and the vacuum pump was turned on to quickly reduce the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 96.5%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 32.8%.

[0096] Comparative Example 5

[0097] The only difference between this comparative example and Example 1 is that no substrate material is used for loading; instead, the polymer is precipitated and then mechanically crushed and ground into an adsorbent. All other steps and parameters remain the same as in Example 1. The specific synthesis steps are as follows:

[0098] Weigh 5.0 g of dry waste polyvinyl chloride powder that has been mechanically pulverized and passed through an 80-mesh sieve, and add it to a three-necked flask containing 100 mL of N,N-dimethylformamide. Stir the mixture in a 60°C water bath with a magnetic stirrer at 400 rpm for approximately 30 minutes until completely dissolved, obtaining a homogeneous and transparent waste plastic dispersion. Add 1.5 g of the rigid crosslinking agent biphenyl to this dispersion, raise the system temperature to 65°C, and maintain the temperature with stirring for 1.5 hours. Add 1.0 g of anhydrous zinc chloride, a Lewis acid catalyst, to the solution, raise the temperature to 75°C, and reflux under nitrogen protection for 1 hour to obtain a dark brown porous polymerization precursor solution. Lower the reaction system temperature to 60°C and slowly add 5.0 g of biphenyl... After adding g of highly active amination reagent tetraethylenepentamine, the reaction was continued at 60°C under reflux for 3 hours to obtain an amination solution. This solution was then slowly poured into a vigorously stirred ethanol / water coagulation bath, causing the polymer to precipitate out as a flocculent precipitate. The precipitate was collected by filtration, dried under vacuum at 60°C for 12 hours, and then ground and sieved using a mechanical grinder to collect granular / powdered adsorbent with a particle size of 60–80 mesh.

[0099] 50 mg of membrane adsorbent was taken and its static CO2 adsorption capacity was determined at 0℃ and 1 bar atmospheric pressure. The adsorption capacity of the material was found to be 1.92 mmol / g, and the adsorption half-saturation time was 35 min. 0.5 g of membrane adsorbent was assembled and packed into a fixed-bed adsorption tower. Air was introduced at a flow rate of 250 mL / min at 25℃ and 101 kPa atmospheric pressure. Low-partial-pressure carbon dioxide was rapidly captured using the amine active sites on the membrane surface until CO2 breakthrough was detected at the outlet concentration, with a breakthrough time of 11.2 min. Figure 7 The integral of Comparative Example 5 showed that the adsorption capacity at a concentration of 460 ppm CO2 was 1.15 mmol / g. Subsequently, vacuum desorption was performed. The gas inlet was stopped and the vacuum pump was turned on to quickly draw the pressure of the fixed bed to negative pressure, so that the adsorbate could be desorbed quickly. The desorption rate was calculated to be 94.3%. After the desorption was complete, air was introduced to restore the pressure in the column to atmospheric pressure and the next cycle was performed. The cycle retention rate after 20 cycles was 92.0%.

[0100] Table 1: The synthesis steps of each embodiment and comparative example are shown in the table below.

[0101]

[0102] Table 2: Performance comparison of each embodiment and comparative example in the direct air capture process is shown in the table below.

[0103]

[0104] The process conditions for each embodiment and comparative example are shown in Table 1, and the performance parameters are shown in Table 2. The "mass ratio" in Table 1 refers to the mass ratio of the added component (rigid crosslinking agent, catalyst, or amination reagent) to the chlorinated plastic. As can be seen from Tables 1 and 2, the carbon dioxide adsorbent based on chlorinated waste plastic of the present invention, when used for direct air capture of carbon dioxide, can achieve a static CO2 adsorption capacity of 2.35–2.51 mmol / g and a dynamic CO2 adsorption capacity of 1.36–1.72 mmol / g (DAC). After initial saturation adsorption, the carbon dioxide desorption rate under vacuum conditions reaches over 98.9%. After 20 adsorption-desorption cycles, the saturated adsorption capacity still reaches over 97.2% of the initial saturated adsorption capacity. Therefore, the carbon dioxide adsorbent based on chlorinated waste plastic of the present invention has extremely high development, promotion, and application value.

Claims

1. A method for producing a film-shaped carbon dioxide adsorbent, characterized by, The method comprises the following steps: S1, dissolving: the crushed chloroplast is added to an organic solvent, heated to 55-65 DEG C, and stirred to completely dissolve the chloroplast, to obtain a waste plastic dispersion liquid; S2, crosslinking: a rigid crosslinking agent is added to the waste plastic dispersion liquid, stirred and aged at 60-70 DEG C for 1-2 h, to obtain a crosslinked plastic solution; S3, preparation of precursor solution: a catalyst is added to the crosslinked plastic solution, heated to reflux at 60-80 DEG C for 0.5-1 h, to obtain a precursor solution; S4, amination: an amination reagent is added to the precursor solution, heated to reflux at 55-65 DEG C for 2-4 h, to obtain an aminated plastic solution; S5, loading: the substrate material is immersed in the aminated plastic solution for 10-30 min; S6, drying: after loading, the substrate material loaded with the aminated plastic is taken out, immersed in a phase separation reagent for 0.1-1 h, and vacuum dried at 50-80 DEG C, to obtain the film-shaped carbon dioxide adsorbent.

2. The method of claim 1, wherein, The chloroplast is polyvinyl chloride, the organic solvent is a polar aprotic solvent, and the mass of the chloroplast to the volume of the organic solvent is 1 g:(5-100) mL.

3. The method of claim 1, wherein, The rigid crosslinking agent is at least one selected from biphenyl, terphenyl, naphthalene, anthracene, trialkene, p-dichlorobenzyl, p-phenylenediamine, melamine, trimeric hydrogen chloride, 4,4'-diaminodiphenyl methane, trialkene, spirobifluorene, tetraphenylmethane, 1,3,5-triphenylbenzene and hexamethylene tetramine, and the mass ratio of the rigid crosslinking agent to the chloroplast is 0.1-1.

5.

4. The method of claim 1, wherein, The catalyst is at least one selected from Lewis acid catalyst and phase transfer catalyst, the Lewis acid catalyst is at least one selected from zinc chloride, iron chloride, aluminum chloride, tin chloride, titanium chloride, copper chloride, cobalt chloride, nickel chloride, antimony trichloride, antimony pentachloride and boron trifluoride ether, the phase transfer catalyst is at least one selected from tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, tetraoctylammonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, polyethylene glycol-400, polyethylene glycol-600, and the mass ratio of the catalyst to the chloroplast is 0.05-1.

5. The method of claim 1, wherein, The amination reagent is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, tris(2-aminoethyl)amine and polyallylamine, and the mass ratio of the amination reagent to the chloroplast is 0.2-5.

6. The method of claim 1, wherein, The substrate material is at least one selected from porous carbon material, inorganic oxide or silicate material and structured skeleton material, the porous carbon material is at least one selected from activated carbon powder, activated carbon fiber, carbon nanotube, graphene, graphene oxide and biochar, the inorganic oxide or silicate material includes at least one selected from mesoporous silica, fumed silica, silica gel, alumina, zeolite molecular sieve, diatomite, bentonite and kaolin, and the structured skeleton material is at least one selected from glass fiber, ceramic honeycomb, foam metal and stainless steel mesh.

7. The method of claim 1, wherein, The phase separation reagent is water, ethanol or a mixture of both.

8. A film-shaped carbon dioxide adsorbent, characterized by, The membrane-shaped carbon dioxide adsorbent is prepared by the method according to any one of claims 1-7.

9. Use of the membrane-shaped carbon dioxide adsorbent according to claim 8 for carbon dioxide capture.

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