Polyacrylate spherical materials, methods of drop sphere formation and applications thereof, and fixed bed co2 sorbents

Abstract

The application provides a polyacrylate spherical material, a drop ball forming method and application thereof, and a fixed bed CO2 adsorbent, the drop ball forming method comprising the following steps: firstly, adding two or three organic monomers into an organic dispersed phase; then, adding an emulsifier, an initiator and a co-emulsifier into the organic dispersed phase in sequence to form a uniform organic phase; mixing a silica sol solution and deionized water to form an aqueous phase; dropping the aqueous phase into the organic phase to perform sufficient emulsification, and then adding a reducing agent to obtain a forming emulsion; using a drop ball forming device to perform drop ball forming and aging on the forming emulsion, and then drying the small balls after aging to obtain finished products. The drop ball forming method can form balls in one step, and has the advantages of simple operation process, green environmental protection, easy industrialization and high yield. Compared with an emulsion suspension polymerization method, the yield of the drop ball forming method can be increased by more than 30%, and the production cost is reduced. The polyacrylate spherical material prepared has the characteristics of high bulk ratio, large particle size and high mechanical strength, and is suitable for being used as a solid adsorbent carrier for fixed bed CO2 adsorption.

Description

Technical Field

[0001] This invention relates to a polyacrylate spherical material, its droplet forming method and application, and a fixed-bed CO2 adsorbent, belonging to the field of CO2 adsorption and capture technology. Background Technology

[0002] The greenhouse effect and global warming are current global hot issues, with CO2 being the most significant anthropogenic gas contributing to the greenhouse effect. Large-scale CO2 capture is a major way to substantially reduce greenhouse gas emissions.

[0003] Regarding CO2 capture, the most mature technology at present is chemical absorption, which has advantages such as fast absorption, mature process, and large processing capacity. However, it also has many drawbacks, including high regeneration energy consumption, limited room for further energy saving and consumption reduction, complex process, and easy equipment corrosion. In contrast, chemical adsorption has many advantages such as low energy consumption, simple process, and no equipment corrosion. Solid adsorbents include calcium-based adsorbents, metal-organic frameworks (MOFs), zeolites, hypercrosslinked polymers, carbon materials, alkali metal carbonates, and amine-functionalized adsorbents. Among them, polymer materials prepared by emulsion template method have high porosity, certain mechanical strength, and a three-dimensional interconnected pore structure with pore size ranging from 0.1 to 300 μm. The pore size can be adjusted to be appropriate and the pore size distribution uniform. These characteristics make emulsion template polymers a prominent advantage as solid adsorbent carriers.

[0004] CN106589201A discloses a method for hydrophilic modification of polystyrene-based materials and its products. This method involves chloromethylating the surface of polystyrene microspheres to bond PVA to the surface, reducing the specific adsorption of biomolecules. Furthermore, PVA contains a large number of hydroxyl groups, facilitating the coupling of specific ligands to meet different separation mode requirements. However, the hydrophilic modification process is complex, involves cumbersome steps, and is difficult to control.

[0005] CN111825796A discloses a polyacrylate composite material for CO2 adsorption and its preparation method. In the preparation process, a polymer emulsion is added to the dispersed phase and dispersed into spheres at a certain rotation speed. After stabilization, a reducing agent is added, and after curing, the spheres are separated and dried to obtain spherical porous polyacrylate microspheres. These microspheres are then subjected to amination grafting and epoxy resin surface end-capping treatment to obtain the polyacrylate composite material for CO2 adsorption.

[0006] CN114213581A discloses a method for preparing hydrophilic polyacrylate crosslinked microspheres. In this method, hydrophilic substances are chemically bonded to comonomers, and then copolymerized with crosslinking agents in an aqueous phase containing stabilizers to form polymer microspheres.

[0007] The above methods all employ emulsion suspension polymerization to prepare polyacrylate microspheres. Although emulsion suspension polymerization has been widely used industrially, the particle size of the resulting microspheres mainly depends on the stirring speed during polymerization. Therefore, the particle size distribution range is wide but can only be controlled within a narrow range, and the yield is low. Furthermore, existing technologies can also prepare polyacrylate microspheres via precipitation polymerization, but precipitation polymerization has very low production efficiency and lacks prospects for large-scale industrial production.

[0008] Therefore, providing a novel polyacrylate spherical material (polyacrylate cross-linked porous spherical particle material) and its droplet forming method and application, as well as a fixed-bed CO2 adsorbent, has become an urgent technical problem to be solved in this field. Summary of the Invention

[0009] To address the aforementioned shortcomings and deficiencies, one objective of this invention is to provide a method for forming droplets of polyacrylate spherical materials.

[0010] Another object of the present invention is to provide a polyacrylate spherical material, which is obtained by the drop ball forming method of the polyacrylate spherical material described above.

[0011] Another object of the present invention is to provide the application of the above-described polyacrylate spherical material as a solid adsorbent carrier for fixed-bed CO2 adsorption.

[0012] Another object of the present invention is to provide a fixed-bed CO2 adsorbent, wherein the adsorption carrier is the polyacrylate spherical material described above.

[0013] To achieve the above objectives, in one aspect, the present invention provides a method for forming droplets of polyacrylate spherical materials, wherein the method for forming droplets of polyacrylate spherical materials includes:

[0014] Step 1: First, add two or three organic monomers to the organic dispersed phase, and then add emulsifier, initiator and co-emulsifier in sequence to form a homogeneous organic phase;

[0015] Step 2: Mix the silica sol solution and deionized water to form an aqueous phase;

[0016] Step 3: After fully emulsifying the aqueous phase by adding dropwise to the organic phase, a reducing agent is added to obtain a formed emulsion;

[0017] Step 4: The emulsion is drop-shaped and aged using a drop-ball forming device, and then the aged balls are dried to obtain the polyacrylate spherical material.

[0018] As a specific embodiment of the drop ball forming method described above in this invention, the organic monomer includes two or three organic monomers selected from glycidyl methacrylate, tert-butyl methacrylate, trimethylolpropane triacrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, styrene, and ethylene glycol dimethacrylate.

[0019] In a specific embodiment of the drop ball forming method described above in this invention, the organic monomers include glycidyl methacrylate, tert-butyl methacrylate, and trimethylolpropane triacrylate in a mass ratio of 2-3.5:0.5-1.5:1.5-3.

[0020] In this invention, the amount of organic dispersed phase affects the yield, dispersion, and mechanical strength of the final polyacrylate spherical material. The volume fraction of the organic dispersed phase only needs to ensure sufficient dissolution and dispersion of all organic monomers. In a specific embodiment of the droplet forming method described above, the volume fraction of the organic dispersed phase is 30-50%, with the total volume of the organic phase being 100%.

[0021] As a specific embodiment of the droplet forming method described above in this invention, the organic dispersed phase includes one or a combination of several of cyclohexane, toluene, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, and ethyl acetate; preferably, one or a combination of several of toluene, cyclohexane, and ethyl acetate.

[0022] As a specific embodiment of the drop ball forming method described above in this invention, the amounts of emulsifier, initiator and co-emulsifier are 3-15%, 1-5% and 1-3% respectively, based on the total weight of 2 or 3 organic monomers as 100%.

[0023] As a specific embodiment of the drop ball forming method described above in this invention, the emulsifier includes one or a combination of several of the following: Span 80, Span 60, Span 20, and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123).

[0024] As a specific embodiment of the drop ball forming method described above in this invention, the initiator includes one or a combination of several of the following: ammonium persulfate, potassium persulfate, benzoyl peroxide, dicumyl peroxide, tert-butyl peroxide, azobisisobutyronitrile, and azobisisovalerate.

[0025] In one specific embodiment of the droplet forming method described above in this invention, the co-emulsifier includes one or a combination of several of hexadecyl alcohol, hexanol, octanol, and p-nonylphenol.

[0026] In one specific embodiment of the droplet forming method described above in this invention, a uniform organic phase can be formed by ultrasound in step one. Furthermore, this invention does not impose specific requirements on the ultrasound duration, which can be reasonably adjusted according to the actual on-site operation. For example, in some embodiments of this invention, the ultrasound duration can be 5-10 minutes.

[0027] In a specific embodiment of the droplet forming method described above in this invention, the mass ratio of silica sol solution to deionized water is 1:1 to 1:4, and the mass concentration of silica sol solution is 25-35%, preferably 30%.

[0028] In a specific embodiment of the drop ball forming method described above in this invention, the aqueous phase is dropped into the organic phase to carry out full emulsification, with the aqueous phase accounting for 55-62% of the total volume of the emulsion obtained after full emulsification.

[0029] As a specific embodiment of the droplet forming method of the present invention, step three, in which the aqueous phase is dropped into the organic phase for thorough emulsification and then a reducing agent is added, specifically includes:

[0030] Under the condition of stirring at a speed of 1000-3000 r / min in a high-speed stirrer, the aqueous phase is dropped into the organic phase. After the addition is completed, the speed is increased to 5000-10000 r / min and stirred for 5-10 min to fully emulsify. Then, a reducing agent is added to the fully emulsified emulsion and stirring is continued for 1-2 min.

[0031] In a specific embodiment of the droplet forming method described above in this invention, the amount of reducing agent is 5-15%, based on the total weight of 2 or 3 organic monomers being 100%.

[0032] As a specific embodiment of the drop ball forming method described above in this invention, the reducing agent includes one or a combination of several of N,N-dimethylaniline, N,N,N,N-tetramethylethylenediamine, ferrous sulfate, and sodium sulfite.

[0033] As a specific embodiment of the droplet forming method described above in this invention, in order to delay the occurrence of polymerization reaction before forming, the process of preparing the forming emulsion must be carried out under low temperature conditions, that is, step three is carried out in a low temperature environment so that the temperature of the forming emulsion drops to below 5°C; preferably, steps one to three are carried out in a low temperature environment.

[0034] In a specific embodiment of the drop ball forming method described above in this invention, the drop ball forming device includes a forming emulsion storage tank, a peristaltic pump, and a forming column. The forming column is a jacketed glass tube with openings at both the upper and lower ends. A dropping plate is provided on the upper opening of the jacketed glass tube, and multiple drop ball forming needles are provided on the dropping plate facing the upper opening. The lower opening of the jacketed glass tube is connected to the forming tank. The outlet of the forming emulsion storage tank is connected to the inlet of the dropping plate via a pipeline through the peristaltic pump.

[0035] In one specific embodiment of the drop ball forming method described above in this invention, a valve is provided between the lower opening of the jacketed glass tube and the inlet of the forming tank.

[0036] In one specific embodiment of the drop ball forming method described above in this invention, the forming emulsion storage tank, peristaltic pump, jacketed glass tube, dropping plate, drop ball forming needle, and forming vessel are all conventional equipment that can be obtained commercially or by self-manufacturing. For example, in some embodiments of this invention, the forming vessel may be a conical flask.

[0037] In a specific embodiment of the drop ball forming method described above in this invention, step four, which involves using a drop ball forming device to perform drop ball forming and aging of the emulsion, includes:

[0038] An aqueous solution of a dispersant, preferably an aqueous solution of a dispersant, is added into the jacketed glass tube so that both the jacketed glass tube and the forming tank are filled with the aqueous solution of the dispersant, and the mixture is heated to 55-70°C by connecting a water bath device through the jacket.

[0039] The molding emulsion is delivered to the drip tray by a peristaltic pump and dripped into the jacketed glass tube through a dropper forming needle. Under the action of surface tension in water, the molding emulsion forms spheres and undergoes polymerization and preliminary solidification to quickly form small balls. The pre-solidified small balls fall into the molding tank and are aged at 55-65℃, that is, the polymerization reaction is fully carried out in the molding tank to ensure that the small balls are completely formed, resulting in aged small balls.

[0040] In some embodiments of the present invention, step four involves using a drop-ball forming device to perform drop-ball forming and aging of the molded emulsion, specifically including:

[0041] Open the valve between the lower opening of the jacketed glass tube and the inlet of the molding tank, and add an aqueous solution of dispersant, preferably an aqueous solution of dispersant, into the jacketed glass tube so that both the jacketed glass tube and the molding tank are filled with the aqueous solution of dispersant, and heat it to 55-70°C by connecting the jacket to a water bath device.

[0042] The molding emulsion is delivered to the drip tray by a peristaltic pump and dripped into the jacketed glass tube through a dropper forming needle. Under the action of surface tension in water, the molding emulsion forms spheres and undergoes polymerization and preliminary solidification to quickly form small balls. The pre-solidified small balls fall into the molding tank and are aged at 55-65℃, that is, the polymerization reaction is fully carried out in the molding tank to ensure that the small balls are completely formed, and the aged small balls are obtained.

[0043] After aging is complete, close the valve between the lower opening of the jacketed glass tube and the inlet of the molding tank, remove the molding tank, take out the aged balls, and then dry the balls.

[0044] In the droplet forming method described above in this invention, the forming emulsion can be formed into spheres through surface tension in either pure water or an aqueous solution of a dispersant. However, the use of a dispersant can further prevent the formed spheres from sticking together. If a dispersant is not used, monodisperse spheres cannot be obtained.

[0045] In one specific embodiment of the droplet forming method of the present invention, the mass concentration of the aqueous solution of the dispersant is 0.13-0.3%, preferably 0.13-0.23%.

[0046] As a specific embodiment of the droplet forming method described above in this invention, the dispersant includes organic dispersants such as polyvinyl alcohol (PVA) and / or polyethylene glycol, preferably polyvinyl alcohol (PVA).

[0047] In one specific embodiment of the droplet forming method described above in this invention, the height of the jacketed glass tube is 1-2m.

[0048] In one specific embodiment of the drop ball forming method described above in this invention, the inner diameter of the drop ball forming needle is 0.3-1 mm.

[0049] In one specific embodiment of the drop ball forming method described above in this invention, the dripping rate is 1-3 drops / second.

[0050] In the droplet forming method described above in this invention, the temperature inside the forming tank needs to be controlled at 55-65℃ to age the pre-cured microspheres at this temperature. The aging time can be adjusted according to the actual needs of the on-site operation. In some embodiments of this invention, the aging time may be, for example, 15-20 minutes.

[0051] In one specific embodiment of the droplet forming method described above, the drying process involves drying at 40-80°C for 4-8 hours. Drying is a standard operation and can be performed in an oven.

[0052] On the other hand, the present invention also provides a polyacrylate spherical material, wherein the polyacrylate spherical material is obtained by the drop ball forming method of the polyacrylate spherical material described above.

[0053] As a specific embodiment of the polyacrylate spherical material described above in this invention, the particle size of the polyacrylate spherical material is 0.85-2 mm, and the bulk density is >0.2 g / mL.

[0054] In another aspect, the present invention also provides the application of the above-described polyacrylate spherical material as a solid adsorbent carrier for fixed-bed CO2 adsorption.

[0055] In another aspect, the present invention also provides a fixed-bed CO2 solid adsorbent, comprising a solid adsorbent carrier and an adsorption active component loaded on the surface of the solid adsorbent carrier, wherein the solid adsorbent carrier is the polyacrylate spherical material described above.

[0056] This invention does not impose specific requirements on the adsorption active components and their dosage used in the fixed-bed CO2 solid adsorbent, which can be reasonably adjusted according to the actual needs of on-site operations. For example, in some embodiments of this invention, the adsorption active component may be an organic amine such as pentaethylenehexamine.

[0057] Compared with the prior art, the beneficial technical effects achieved by the present invention include:

[0058] The present invention provides a method for drop ball forming of polyacrylate spherical materials. First, two or three organic monomers are added to an organic dispersed phase. Then, an emulsifier, an initiator, and a co-emulsifier are added sequentially to form a homogeneous organic phase. Subsequently, a silica sol solution and deionized water are mixed to form an aqueous phase. The aqueous phase is then dropped into the organic phase for thorough emulsification. A reducing agent is added to obtain a water-in-oil molding emulsion with a density greater than that of water. Finally, the molding emulsion is formed using a top-down drop ball forming method. Polyacrylate spherical materials are obtained by utilizing the surface tension of the molding emulsion in water and the polymerization reaction that occurs within it.

[0059] Compared with traditional precipitation polymerization and suspension polymerization methods, the droplet forming method for polyacrylate spherical materials provided by this invention has the following advantages:

[0060] (1) It can form balls in one step without secondary molding. The operation process is simple, green and environmentally friendly, easy to industrialize, and has a high yield. Its yield can be increased by more than 30% compared with the emulsion suspension polymerization method, which reduces the production cost.

[0061] (2) The operating conditions are mild, and it can be polymerized and molded at a low temperature without the need for high-temperature calcination;

[0062] (3) The prepared polyacrylate spherical material has the characteristics of high bulk density and large particle size, with a particle size of 0.85-2 mm and a bulk density of >0.2 g / mL, and is suitable as a solid adsorbent carrier for fixed bed CO2 adsorption.

[0063] (4) The obtained polyacrylate spherical material has high sphericity, easy particle size control and uniform particle size distribution.

[0064] (5) The addition of hydrophilic silica sol makes the prepared polyacrylate spherical material have higher mechanical strength. Compared with the existing emulsion suspension polymerization method, the mechanical strength of the polyacrylate spherical material can be increased by more than 15%, and it is not easy to wear during fixed bed operation. Attached Figure Description

[0065] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0066] Figure 1 This is a schematic diagram of the structure of the drop ball forming device used in the embodiments of the present invention.

[0067] Figure 2 This is a physical image of the polyacrylate spherical material provided in Embodiment 2 of the present invention.

[0068] Figure 3 This is a physical image of the polyacrylate spherical material provided in Embodiment 5 of the present invention.

[0069] Figure 4 This is a physical image of the polyacrylate spherical material provided in Comparative Example 2 of the present invention.

[0070] Figure 5 This is a physical image of the polyacrylate spherical material provided in Comparative Example 5 of the present invention.

[0071] Figure 6 This is a physical image of the polyacrylate spherical material provided in Comparative Example 7 of the present invention.

[0072] Figure 7 A scanning electron microscope image (500 μm) of the polyacrylate spherical material provided in Example 1 of the present invention.

[0073] Figure 8 A scanning electron microscope image (3.00 μm) of the polyacrylate spherical material provided in Example 1 of the present invention.

[0074] Explanation of main icon numbers:

[0075] 1. Molded emulsion storage tank;

[0076] 2. Peristaltic pump;

[0077] 3. Drip tray;

[0078] 31. Droplet forming needle

[0079] 4. Molding column;

[0080] 5. Molding tank;

[0081] 6. Aqueous solutions of dispersants. Detailed Implementation

[0082] It should be noted that the term "comprising" and any variations thereof in the specification, claims, and accompanying drawings of this invention are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or devices.

[0083] The "range" disclosed in this invention is given in the form of a lower limit and an upper limit. It can be one or more lower limits and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges defined in this way are composable, meaning that any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for specific parameters, it is also expected that ranges of 60-110 and 80-120 are also expected. Furthermore, if the listed minimum range values ​​are 1 and 2, and the listed maximum range values ​​are 3, 4, and 5, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0084] In this invention, unless otherwise specified, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this invention, and "0-5" is simply a shortened representation of these numerical combinations.

[0085] In this invention, unless otherwise specified, all embodiments and preferred embodiments mentioned in this invention can be combined with each other to form new technical solutions.

[0086] In this invention, unless otherwise specified, all technical features and preferred features mentioned in this invention can be combined with each other to form new technical solutions.

[0087] In this invention, unless otherwise specified, the term "two kinds" as used in this specification means "at least two kinds".

[0088] In this invention, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0089] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying tables, drawings, and embodiments. The embodiments described below are some, but not all, embodiments of this invention, and are only used to illustrate the invention, and should not be considered as limiting the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0090] Example 1

[0091] This embodiment provides a polyacrylate spherical material, which is obtained by a drop ball forming method including the following specific steps:

[0092] Step 1: Weigh 2.1g glycidyl methacrylate, 0.8g tert-butyl methacrylate and 2.1g trimethylolpropane triacrylate and add them to toluene, which accounts for 30% of the total volume of the organic phase. Then add 0.3g P123, 0.2g benzoyl peroxide (BPO) and 0.1g hexadecyl alcohol in sequence. Then sonicate in an ultrasonic cleaner for 5 minutes to dissolve and mix evenly, which is the oil phase, i.e., the homogeneous organic phase.

[0093] Step 2: Weigh 7g of a 35% silica sol solution and mix it with 13g of deionized water to form the aqueous phase.

[0094] Step 3: Place the dissolved oil phase in an ice bath. With the water phase accounting for 56% of the total volume of the emulsion after full emulsification, slowly add the well-stirred water phase dropwise to the oil phase at a high speed of 3000 r / min. After the water phase is added, increase the speed to 7000 r / min and stir for another 5 minutes to fully emulsify. Then add 0.3 g of reducing agent N,N-dimethylaniline and continue stirring for 1 minute to obtain a stable water-in-oil emulsion, i.e., the formed emulsion.

[0095] Step 4: The emulsion is subjected to drop ball forming and aging using a drop ball forming device, wherein a schematic diagram of the drop ball forming device is shown below. Figure 1 As shown, from Figure 1 As can be seen, it includes a molding emulsion storage tank 1, a peristaltic pump 2, and a molding column 4 with a height of 1.2m. The molding column 4 is a jacketed glass tube with openings at both the top and bottom. A drip plate 3 is provided on the upper opening of the jacketed glass tube. Multiple drop ball forming needles 31 are provided on the side of the drip plate 3 facing the upper opening. The lower opening of the jacketed glass tube is connected to the molding tank 5. The outlet of the molding emulsion storage tank 1 is connected to the inlet of the drip plate 3 through a pipeline via the peristaltic pump 2.

[0096] Droplet forming and aging specifically include:

[0097] Prepare an aqueous solution 6 of the dispersant, which in this embodiment is an aqueous solution of polyvinyl alcohol with a mass concentration of 0.13%, and pour it into the molding column. Then, connect it to a water bath device, such as a water bath circulating heater, and heat it to 60°C. The molding tank, such as a conical flask, is heated at 55°C using a magnetic stirring heater to ensure that the small balls are completely formed.

[0098] The molding emulsion is pumped into the dropping tray at a speed of 5.5 r / min using a peristaltic pump. The emulsion is then dropped into an aqueous solution of polyvinyl alcohol contained in a jacketed glass tube at a dropping rate of 1 drop / second using a dropping ball forming needle with an inner diameter of 0.3 mm. Under the action of surface tension in the water, the molding emulsion forms spheres and undergoes polymerization and preliminary curing. The pre-cured spheres fall into the molding tank and are aged at 55°C for 15 min to obtain aged spheres.

[0099] The small balls were removed and dried in an oven at 50°C for 6 hours to prepare macroporous polymer balls, namely the polyacrylate spherical material.

[0100] Example 2

[0101] This embodiment provides a polyacrylate spherical material, which is obtained by a drop ball forming method including the following specific steps:

[0102] Step 1: Weigh 2.2g glycidyl methacrylate, 1.0g tert-butyl methacrylate and 1.6g trimethylolpropane triacrylate and add them to toluene, which accounts for 35% of the total volume of the organic phase. Then add 0.4g SPAN80, 0.1g ammonium persulfate and 0.12g hexanol in sequence. Then sonicate in an ultrasonic cleaner for 7 minutes to dissolve and mix evenly, which is the oil phase, i.e., the homogeneous organic phase.

[0103] Step 2: Weigh 7g of silica sol solution with a mass concentration of 32% and mix it with 13g of deionized water to form the aqueous phase;

[0104] Step 3: Place the dissolved oil phase in an ice bath. With a high-speed mixer at 2000 rpm, slowly add the water phase dropwise to the oil phase, making up 57% of the total volume of the emulsion after full emulsification. After the water phase is added, increase the speed to 8000 rpm and stir for 6 minutes to fully emulsify. Then add 0.4 g of reducing agent N,N,N,N-tetramethylethylenediamine and continue stirring for 1 minute to obtain a stable water-in-oil emulsion, i.e., the formed emulsion.

[0105] Step 4: The emulsion is subjected to drop ball forming and aging using a drop ball forming device, wherein a schematic diagram of the drop ball forming device is shown below. Figure 1 As shown, from Figure 1 As can be seen, it includes a molding emulsion storage tank 1, a peristaltic pump 2, and a molding column 4 with a height of 1.2m. The molding column 4 is a jacketed glass tube with openings at both the top and bottom. A drip plate 3 is provided on the upper opening of the jacketed glass tube. Multiple drop ball forming needles 31 are provided on the side of the drip plate 3 facing the upper opening. The lower opening of the jacketed glass tube is connected to the molding tank 5. The outlet of the molding emulsion storage tank 1 is connected to the inlet of the drip plate 3 through a pipeline via the peristaltic pump 2.

[0106] Droplet forming and aging specifically include:

[0107] Prepare an aqueous solution 6 of the dispersant, which in this embodiment is an aqueous solution of polyethylene glycol with a mass concentration of 0.15%, and pour it into the molding column. Then, connect it to a water bath device, such as a water bath circulating heater, and heat it to 70°C. The molding tank, such as a conical flask, is heated at 58°C using a magnetic stirring heater to ensure that the small balls are completely formed.

[0108] The molding emulsion is pumped into the dropping tray at a speed of 4.5 r / min using a peristaltic pump. The emulsion is then dropped into an aqueous solution of polyethylene glycol in a jacketed glass tube at a dropping rate of 1 drop / second using a 0.3 mm inner diameter ball forming needle. Under the action of surface tension in the water, the molding emulsion forms spheres and undergoes polymerization and preliminary curing. The pre-cured spheres fall into the molding tank and are aged at 58°C for 15 min to obtain aged spheres.

[0109] The small balls were removed and dried in an oven at 65°C for 6 hours to prepare macroporous polymer balls, namely the polyacrylate spherical material.

[0110] Example 3

[0111] This embodiment provides a polyacrylate spherical material, which is obtained by a drop ball forming method including the following specific steps:

[0112] Step 1: Weigh 2.3g glycidyl methacrylate, 1.2g tert-butyl methacrylate and 2.5g trimethylolpropane triacrylate and add them to toluene, which accounts for 40% of the total volume of the organic phase. Then add 0.2g SPAN 60, 0.24g dicumyl peroxide and 0.18g octanol in sequence. Then sonicate in an ultrasonic cleaner for 8 minutes to dissolve and mix evenly, which is the oil phase, i.e., the homogeneous organic phase.

[0113] Step 2: Weigh 8g of a 28% silica sol solution and mix it with 12g of deionized water to form the aqueous phase;

[0114] Step 3: Place the dissolved oil phase in an ice bath. With the water phase accounting for 59% of the total volume of the emulsion after full emulsification, slowly add the well-stirred water phase dropwise to the oil phase at a high speed of 3000 r / min. After the water phase is added, increase the speed to 9000 r / min and stir for 7 minutes to fully emulsify. Then add 0.6 g of reducing agent ferrous sulfate and continue stirring for 1 minute to obtain a stable water-in-oil emulsion, i.e., the formed emulsion.

[0115] Step 4: The emulsion is subjected to drop ball forming and aging using a drop ball forming device, wherein a schematic diagram of the drop ball forming device is shown below. Figure 1 As shown, from Figure 1 As can be seen, it includes a molding emulsion storage tank 1, a peristaltic pump 2, and a molding column 4 with a height of 1.2m. The molding column 4 is a jacketed glass tube with openings at both the top and bottom. A drip plate 3 is provided on the upper opening of the jacketed glass tube. Multiple drop ball forming needles 31 are provided on the side of the drip plate 3 facing the upper opening. The lower opening of the jacketed glass tube is connected to the molding tank 5. The outlet of the molding emulsion storage tank 1 is connected to the inlet of the drip plate 3 through a pipeline via the peristaltic pump 2.

[0116] Droplet forming and aging specifically include:

[0117] Prepare an aqueous solution 6 of the dispersant, which in this embodiment is an aqueous solution of polyvinyl alcohol with a mass concentration of 0.18%, and pour it into the molding column. Then, connect it to a water bath device, such as a water bath circulating heater, and heat it to 55°C. The molding tank, such as a conical flask, is heated at 60°C using a magnetic stirring heater to ensure that the small balls are completely formed.

[0118] The molding emulsion is pumped into the dropping tray at a speed of 7.5 r / min using a peristaltic pump. The emulsion is then dropped into an aqueous solution of polyvinyl alcohol contained in a jacketed glass tube at a dropping rate of 2 drops / second using a dropping ball forming needle with an inner diameter of 0.8 mm. Under the action of surface tension in the water, the molding emulsion forms spheres and undergoes polymerization and preliminary curing. The pre-cured spheres fall into the molding tank and are aged at 60°C for 15 min to obtain aged spheres.

[0119] The small balls were removed and dried in an oven at 70°C for 6 hours to prepare macroporous polymer balls, namely the polyacrylate spherical material.

[0120] Example 4

[0121] This embodiment provides a polyacrylate spherical material, which is obtained by a drop ball forming method including the following specific steps:

[0122] Step 1: Weigh 2.6g glycidyl methacrylate, 1.3g tert-butyl methacrylate and 2.8g trimethylolpropane triacrylate and add them to a mixture of cyclohexane and ethyl acetate accounting for 45% of the total volume of the organic phase. Then add 0.3g SPAN20, 0.2g BPO and 0.08g p-nonylphenol in sequence, and then sonicate in an ultrasonic cleaner for 9 minutes to dissolve and mix evenly, which is the oil phase, i.e., the homogeneous organic phase.

[0123] Step 2: Weigh 7g of a 30% silica sol solution and mix it with 20g of deionized water to form the aqueous phase;

[0124] Step 3: Place the dissolved oil phase in an ice bath. With a high-speed mixer at 3000 rpm, slowly add the water phase dropwise to the oil phase, making sure the water phase accounts for 61% of the total volume of the emulsion after full emulsification. After the water phase is added, increase the speed to 10000 rpm and stir for another 8 minutes to fully emulsify. Then add 0.5 g of reducing agent N,N-dimethylaniline and continue stirring for 1 minute to obtain a stable water-in-oil emulsion, which is the formed emulsion.

[0125] Step 4: The emulsion is subjected to drop ball forming and aging using a drop ball forming device, wherein a schematic diagram of the drop ball forming device is shown below. Figure 1 As shown, from Figure 1As can be seen, it includes a molding emulsion storage tank 1, a peristaltic pump 2, and a molding column 4 with a height of 1.8m. The molding column 4 is a jacketed glass tube with openings at both the top and bottom. A drip plate 3 is provided on the upper opening of the jacketed glass tube. Multiple drop ball forming needles 31 are provided on the side of the drip plate 3 facing the upper opening. The lower opening of the jacketed glass tube is connected to the molding tank 5. The outlet of the molding emulsion storage tank 1 is connected to the inlet of the drip plate 3 through a pipeline via the peristaltic pump 2.

[0126] Droplet forming and aging specifically include:

[0127] Prepare an aqueous solution 6 for the dispersant. In this embodiment, it is a mixed aqueous solution of polyvinyl alcohol and polyethylene glycol with a mass concentration of 0.2%. Pour it into the molding column and then connect it to a water bath device, such as a water bath circulating heater, to heat it to 65°C. The molding tank, such as a conical flask, is heated at 62°C using a magnetic stirring heater to ensure that the small balls are completely formed.

[0128] The molding emulsion is pumped into the dropping tray at a speed of 5.5 r / min using a peristaltic pump. Then, the molding emulsion is dropped into a mixed aqueous solution of polyvinyl alcohol and polyethylene glycol in a jacketed glass tube at a dropping rate of 2 drops / second using a dropping ball forming needle with an inner diameter of 0.3 mm. Under the action of surface tension in the water, the molding emulsion forms spheres and undergoes polymerization and preliminary curing. The pre-cured spheres fall into the molding tank and are aged at 62°C for 15 min to obtain aged spheres.

[0129] The small balls were removed and dried in an oven at 75°C for 6 hours to prepare macroporous polymer balls, namely the polyacrylate spherical material.

[0130] Example 5

[0131] This embodiment provides a polyacrylate spherical material, which is obtained by a drop ball forming method including the following specific steps:

[0132] Step 1: Weigh 3.0g glycidyl methacrylate, 1.5g tert-butyl methacrylate and 2.1g trimethylolpropane triacrylate and add them to a mixture of cyclohexane and ethyl acetate accounting for 50% of the total volume of the organic phase. Then add 0.4g of P123 and 0.3g of SPAN80 as a combined emulsifier, 0.2g of BPO and 0.05g of hexadecyl alcohol and 0.05g of hexanol as a combined co-emulsifier. Then sonicate in an ultrasonic cleaner for 10 minutes to dissolve and mix evenly, which is the oil phase, i.e., the homogeneous organic phase.

[0133] Step 2: Weigh 7g of 25% silica sol solution and mix it with 9g of deionized water to form the aqueous phase;

[0134] Step 3: Place the dissolved oil phase in an ice bath. Under high speed of 3000 rpm, slowly add the aqueous phase dropwise to the oil phase, making up 62% of the total volume of the emulsion after full emulsification. After the addition is complete, increase the speed to 7000 rpm and stir for 9 minutes to fully emulsify. Then add 0.7 g of the combined reducing agent (i.e., 0.3 g of N,N-dimethylaniline, 0.2 g of N,N,N,N-tetramethylethylenediamine, and 0.2 g of sodium sulfite). Continue stirring for 1 minute to obtain a stable water-in-oil emulsion, i.e., the formed emulsion.

[0135] Step 4: The emulsion is subjected to drop ball forming and aging using a drop ball forming device, wherein a schematic diagram of the drop ball forming device is shown below. Figure 1 As shown, from Figure 1 As can be seen, it includes a molding emulsion storage tank 1, a peristaltic pump 2, and a molding column 4 with a height of 1.8m. The molding column 4 is a jacketed glass tube with openings at both the top and bottom. A drip plate 3 is provided on the upper opening of the jacketed glass tube. Multiple drop ball forming needles 31 are provided on the side of the drip plate 3 facing the upper opening. The lower opening of the jacketed glass tube is connected to the molding tank 5. The outlet of the molding emulsion storage tank 1 is connected to the inlet of the drip plate 3 through a pipeline via the peristaltic pump 2.

[0136] Droplet forming and aging specifically include:

[0137] Prepare an aqueous solution 6 of the dispersant, which in this embodiment is an aqueous solution of polyethylene glycol with a mass concentration of 0.3%, and pour it into the molding column. Then, connect it to a water bath device, such as a water bath circulating heater, and heat it to 70°C. The molding tank, such as a conical flask, is heated at 65°C using a magnetic stirring heater to ensure that the small balls are completely formed.

[0138] The molding emulsion is pumped into the dropping tray at a speed of 5.5 r / min using a peristaltic pump. The emulsion is then dropped into an aqueous solution of polyethylene glycol in a jacketed glass tube at a dropping rate of 3 drops / second using a 0.45 mm inner diameter ball forming needle. Under the action of surface tension in the water, the molding emulsion forms spheres and undergoes polymerization and preliminary curing. The pre-cured spheres fall into the molding tank and are aged at 65°C for 15 min to obtain aged spheres.

[0139] The small balls were removed and dried in an oven at 80°C for 6 hours to prepare macroporous polymer balls, namely the polyacrylate spherical material.

[0140] Comparative Example 1

[0141] This comparative example provides a polyacrylate material, which is also prepared by drop ball molding. The only difference between this comparative example and Example 1 is that:

[0142] The amount of emulsifier P123 used is 0.1g.

[0143] Comparative Example 2

[0144] This comparative example provides a polyacrylate material, which is also prepared by drop ball molding. The only difference between this comparative example and Example 2 is that:

[0145] The amount of deionized water used is 30g.

[0146] Comparative Example 3

[0147] This comparative example provides a polyacrylate material, which is also prepared by drop ball molding. The only difference between this comparative example and Example 3 is that:

[0148] The amount of silica sol solution with a mass concentration of 28% is 1g.

[0149] Comparative Example 4

[0150] This comparative example provides a polyacrylate material, which is also prepared by drop ball molding. The only difference between this comparative example and Example 4 is that:

[0151] Water bath equipment, such as a water bath circulating heater, is connected via a jacket to heat to 50°C.

[0152] Comparative Example 5

[0153] This comparative example provides a polyacrylate material, which is also prepared by drop ball molding. The only difference between this comparative example and Example 5 is that:

[0154] The inner diameter of the droplet forming needle is 1.2 mm.

[0155] Comparative Example 6

[0156] This comparative example provides a polyacrylate material prepared by emulsion suspension polymerization, which includes the following specific steps:

[0157] Step 1: Weigh 2.1g glycidyl methacrylate, 0.8g tert-butyl methacrylate and 2.1g trimethylolpropane triacrylate and add them to toluene, which accounts for 30% of the total volume of the organic phase. Then add 0.3g P123, 0.2g benzoyl peroxide (BPO) and 0.1g hexadecyl alcohol in sequence. Then sonicate in an ultrasonic cleaner for 5 minutes to dissolve and mix evenly, which is the oil phase, i.e., the homogeneous organic phase.

[0158] Step 2: Weigh 13g of deionized water as the aqueous phase;

[0159] Step 3: Place the dissolved oil phase in an ice bath. With a high-speed mixer at 3000 rpm, slowly add the aqueous phase dropwise to the oil phase, making up 56% of the total volume of the emulsion after full emulsification. After the addition is complete, increase the speed to 7000 rpm and stir for another 5 minutes to fully emulsify. Then add 0.3 g of reducing agent N,N-dimethylaniline and continue stirring for 1 minute to obtain the final emulsion.

[0160] Step 4: Measure 150 mL of water and add it to a 250 mL three-necked flask, along with 0.15 g of ammonium persulfate and 1.5 mL of polyvinyl alcohol dispersant. Stir the mixture using an electric stirrer at 300 rpm and heat it in a constant temperature water bath at 45 °C. After the temperature is constant for 10 min, add the emulsion prepared in Step 3 to the three-necked flask. Under the action of its own interfacial tension, the emulsion will disperse into spherical shapes. Continue stirring for 10 min, then remove the spheres and dry them in an oven at 60 °C for 6 hours to obtain macroporous polymer spheres, i.e., the polyacrylate material.

[0161] Comparative Example 7

[0162] This comparative example provides a polyacrylate material, which is also prepared by drop ball molding. The only difference between this comparative example and Example 1 is that:

[0163] Instead of adding the dispersant polyvinyl alcohol to the molding liquid, pure water is used as the molding liquid.

[0164] The polyacrylate spherical materials obtained in Examples 1-5 of this invention have a basically consistent appearance, all being regular spherical particles, i.e., possessing high sphericity. Only the appearance images of the polyacrylate spherical materials obtained in Examples 2 and 5 are provided here, as shown in the figures below. Figure 2 and Figure 3 As shown.

[0165] The physical images of the polyacrylate materials provided in Comparative Examples 2, 5, and 7 are shown below. Figure 4 - Figure 6 As shown. From Figure 4 and Figure 5 As can be seen, the polyacrylate materials provided in Comparative Example 2 and Comparative Example 5 have significantly different appearances, mostly consisting of ellipsoidal or irregularly shaped particles with poor sphericity. Figure 6 As can be seen, because Comparative Example 7 used pure water as the molding liquid and did not use a dispersant, the droplets adhered to each other and formed large clumps during the polymerization process, making it impossible to form monodisperse spheres.

[0166] Additionally, the scanning electron microscope image of the polyacrylate spherical material obtained in Example 1 of this invention is shown below. Figure 7 and Figure 8 As shown. From Figure 7 and Figure 8As can be seen, the internal details of the polyacrylate spherical material are revealed, showing a large number of macroporous structures inside.

[0167] Furthermore, the molding effects, bulk density, and mechanical strength of the polyacrylate spherical materials or polyacrylate material samples obtained in Examples 1-5 and Comparative Examples 1-7 of the present invention are shown in Table 1 below.

[0168] Table 1

[0169]

[0170] As can be seen from the molding effect data shown in Table 1 above, the yields of Examples 1-5 of the present invention are high, the molding effect is good, and the particle size is uniform (the higher the yield, the more uniform the particle size). Polyacrylate spherical materials with high bulk density that are suitable for fixed bed processes can be obtained.

[0171] Table 1 also shows that when the amount of emulsifier in Comparative Example 1 was reduced to 2% of the total mass fraction of organic monomers, the emulsion broke down and could not be formed in the molding liquid. This indicates that the amount of emulsifier should be controlled at 3-15% of the total mass fraction of organic monomers and should not be too little.

[0172] Comparative Examples 2 and 3 investigated the mass ratio of silica sol solution to deionized water. The results showed that if too much deionized water was used, the oil and water phases in the emulsion would become unstable and difficult to form, resulting in a yield of 20%. When too little silica sol solution was used, the emulsion density was too low, and it could not fall to form polymers, instead floating to the surface and breaking, thus failing to form polymers. This indicates that the mass ratio of silica sol solution to deionized water should be controlled between 1:1 and 1:4.

[0173] In Comparative Example 4, the polymerization temperature inside the molding column was 50°C. The low polymerization temperature resulted in incomplete droplet formation, leading to experimental failure. This indicates that the polymerization temperature of the present invention should be controlled between 55-65°C.

[0174] The needle size used in Comparative Example 5 was 1.2 mm. As shown in Table 1, the yield of 0.85-2 mm droplets in Comparative Example 5 was only 13.6%, indicating that the larger inner diameter of the droplet forming needle resulted in larger droplet size and a wider distribution range, leading to poorer sphericity (e.g., ...). Figure 5 As shown in the figure, the yield decreased, indicating that in order to ensure that the particle size of the carrier is as uniform as possible, the needle size should be controlled within 0.3-1mm.

[0175] Comparative Example 6 was prepared using the traditional emulsion suspension polymerization method, and the results showed that its yield was only 41%. This indicates that the drop ball forming method provided by the present invention can effectively improve the yield of the obtained polyacrylate spherical material samples and ensure good sphericity.

[0176] As can be seen from Table 1 above, the polyacrylate spherical materials obtained in Examples 1-5 of this invention all exhibit higher mechanical strength. Compared with the existing emulsion suspension polymerization method, the mechanical strength of the polyacrylate spherical materials can be increased by more than 15%, and they are less prone to wear during fixed-bed operation. The higher mechanical strength of the polyacrylate spherical materials obtained in Examples 1-5 of this invention can be attributed to the addition of hydrophilic silica sol.

[0177] Application examples

[0178] To further evaluate the performance of the polyacrylate spherical material samples prepared in the embodiments and comparative examples of this invention as solid adsorbent carriers for fixed-bed CO2 adsorption, this application example uses a physical impregnation method to load a certain amount of organic amine onto the polyacrylate spherical material samples prepared in Examples 1-5 and Comparative Examples 1-6 of this invention and evaluate their adsorption performance. The specific loading steps are as follows: 2g of each of the polyacrylate spherical material samples prepared in Examples 1-5 and Comparative Examples 1-6 are weighed and placed in a round-bottom flask. 15g of pentaethylenehexamine is added, and the samples are impregnated by rotation at 60°C for 6 hours using a rotary evaporator. After impregnation, the samples are washed with a small amount of alcohol and then dried at 40°C for 10 hours. Finally, the CO2 adsorption capacity of the polyacrylate spherical material samples loaded with pentaethylenehexamine is tested using a physical adsorption analyzer at a temperature of 25°C and a pressure of 1 bar. The specific results are shown in Table 2 below.

[0179] Table 2

[0180] Item Adsorption capacity (mmol / g) Item Adsorption capacity (mmol / g) Example 1 4.1 Comparative Example 1 Unshaped Example 2 3.6 Comparative Example 2 2.5 Example 3 3.7 Comparative Example 3 Unshaped Example 4 3.5 Comparative Example 4 Unshaped Example 5 3.4 Comparative Example 5 2.9 Comparative Example 6 3.0 Comparative Example 7 Unshaped

[0181] As can be seen from Table 2 above, under the same conditions, the CO2 adsorption capacity of the polyacrylate spherical material sample prepared in the embodiments of the present invention as a solid adsorbent carrier for fixed-bed CO2 adsorption is significantly higher than that of the polyacrylate spherical material sample prepared in the comparative example. This indicates that the polyacrylate spherical material sample prepared by the drop ball forming method provided by the present invention has superior CO2 adsorption performance.

[0182] The above description is merely a specific embodiment of the present invention and should not be construed as limiting the scope of the invention. Therefore, any substitution of equivalent components or equivalent changes and modifications made within the scope of protection of this patent should still fall within the scope of this patent. Furthermore, the technical features, technical features and technical inventions, and technical inventions in this invention can be freely combined and used.

Claims

1. A method for forming droplets of polyacrylate spherical material, characterized in that, The method for forming droplets of the polyacrylate spherical material includes: Step 1: First, add two or three organic monomers to the organic dispersed phase, and then add emulsifier, initiator and co-emulsifier in sequence to form a homogeneous organic phase; wherein, based on the total weight of the two or three organic monomers as 100%, the amount of emulsifier, initiator and co-emulsifier is 3-15%, 1-5% and 1-3% respectively. The organic monomers include two or three of the following: glycidyl methacrylate, tert-butyl methacrylate, trimethylolpropane triacrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, styrene, and ethylene glycol dimethacrylate. Step 2: Mix the silica sol solution and deionized water to form an aqueous phase; wherein the mass ratio of silica sol solution to deionized water is 1:1 to 1:

4. Step 3: After fully emulsifying the aqueous phase by dripping it into the organic phase, a reducing agent is added to obtain a shaped emulsion; wherein, the reducing agent includes one or a combination of several of N,N-dimethylaniline, N,N,N,N-tetramethylethylenediamine, ferrous sulfate, and sodium sulfite; Step 4: The emulsion is drop-shaped and aged using a drop-ball forming device, and then the aged balls are dried to obtain the polyacrylate spherical material.

2. The droplet forming method according to claim 1, characterized in that, The organic monomers include glycidyl methacrylate, tert-butyl methacrylate, and trimethylolpropane triacrylate in a mass ratio of 2-3.5:0.5-1.5:1.5-3.

3. The droplet forming method according to claim 1, characterized in that, With the total volume of the organic phase being 100%, the volume fraction of the organic dispersed phase is 30-50%.

4. The droplet forming method according to claim 1 or 3, characterized in that, The organic dispersed phase includes one or a combination of several of cyclohexane, toluene, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, and ethyl acetate.

5. The droplet forming method according to claim 4, characterized in that, The organic dispersed phase is one or a combination of toluene, cyclohexane, and ethyl acetate.

6. The droplet forming method according to claim 1, characterized in that, The emulsifier includes one or a combination of several of span80, span60, span20, and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.

7. The droplet forming method according to claim 1, characterized in that, The initiator includes one or a combination of several of the following: ammonium persulfate, potassium persulfate, benzoyl peroxide, dicumyl peroxide, tert-butyl peroxide, azobisisobutyronitrile, and azobisisovalerate.

8. The droplet forming method according to claim 1, characterized in that, The co-emulsifier includes one or a combination of several of hexadecyl alcohol, hexanol, octanol, and p-nonylphenol.

9. The droplet forming method according to claim 1, characterized in that, The mass concentration of the silica sol solution is 25-35%.

10. The droplet forming method according to claim 1, characterized in that, The aqueous phase is added dropwise to the organic phase to ensure complete emulsification, with the aqueous phase comprising 55-62% of the total volume of the emulsion obtained after full emulsification.

11. The droplet forming method according to claim 1, characterized in that, The amount of reducing agent used is 5-15%, based on the total weight of 2 or 3 organic monomers as 100%.

12. The droplet forming method according to claim 1, characterized in that, Step 3 is carried out entirely in a low-temperature environment to reduce the temperature of the molding emulsion to below 5°C.

13. The droplet forming method according to claim 1, characterized in that, The drop ball forming device includes a forming emulsion storage tank, a peristaltic pump, and a forming column. The forming column is a jacketed glass tube with openings at both the top and bottom. A dropping plate is provided on the upper opening of the jacketed glass tube, and multiple drop ball forming needles are provided on the side of the dropping plate facing the upper opening. The lower opening of the jacketed glass tube is connected to the forming tank. The outlet of the forming emulsion storage tank is connected to the inlet of the dropping plate through a pipeline via the peristaltic pump.

14. The droplet forming method according to claim 1 or 13, characterized in that, Step four, which involves using a drop-ball forming device to perform drop-ball forming and aging of the molded emulsion, includes: An aqueous solution of dispersant is added into the jacketed glass tube so that both the jacketed glass tube and the molding tank are filled with the aqueous solution of dispersant, and the mixture is heated to 55-70°C by connecting the jacket to a water bath device. The molding emulsion is delivered to the drip tray by a peristaltic pump and dripped into the jacketed glass tube by a dropper forming needle. Under the action of surface tension in water, the molding emulsion forms spheres and undergoes polymerization and preliminary solidification. The pre-solidified spheres fall into the molding tank and are aged at 55-65℃ to obtain aged spheres.

15. The droplet forming method according to claim 14, characterized in that, The mass concentration of the dispersant in the aqueous solution is 0.13-0.3%.

16. The droplet forming method according to claim 14, characterized in that, The dispersant includes polyvinyl alcohol and / or polyethylene glycol.

17. The droplet forming method according to claim 14, characterized in that, The height of the jacketed glass tube is 1-2m.

18. The droplet forming method according to claim 14, characterized in that, The inner diameter of the droplet forming needle is 0.3-1mm.

19. The droplet forming method according to claim 14, characterized in that, The dripping rate is 1-3 drops / second.

20. A spherical polyacrylate material, characterized in that, The polyacrylate spherical material is obtained by the drop ball forming method of the polyacrylate spherical material according to any one of claims 1-19.

21. The polyacrylate spherical material according to claim 20, characterized in that, The polyacrylate spherical material has a particle size of 0.85-2 mm and a bulk density >0.2 g / mL.

22. The use of the polyacrylate spherical material of claim 20 or 21 as a solid adsorbent carrier for fixed-bed CO2 adsorption.

23. A fixed-bed CO2 solid adsorbent, comprising a solid adsorbent carrier and an adsorption-active component loaded on the surface of the solid adsorbent carrier, characterized in that, The solid adsorbent carrier is the polyacrylate spherical material as described in claim 20 or 21.

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