Polyacrylate microsphere material, droplet sphere forming method and application thereof, and fluidized bed co2 adsorbent

Abstract

The application provides a polyacrylate microsphere material and a drop ball forming method and application thereof, and a fluidized bed CO2 adsorbent. The drop ball forming method of the polyacrylate microsphere material comprises the following steps: first, adding two or three organic monomers into an organic dispersed phase; then, adding an emulsifier, an initiator and an auxiliary emulsifier in sequence to form a uniform organic phase; adding deionized water into the organic phase for 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 drying the small balls after aging to obtain the polyacrylate microsphere material. The drop ball forming method provided by the application has the advantages of simple operation process, green environmental protection, easy industrialization, high yield and low cost. The prepared polyacrylate microsphere material has the characteristics of low bulk ratio, small particle size, high sphericity, easy control of particle size, uniform particle size distribution and high mechanical strength.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of polyacrylate microsphere material and its drop ball forming method and application, fluidized bed CO2 adsorbent, belong to CO2 adsorption capture technical field. BACKGROUND

[0002] Greenhouse effect and climate warming are the current global hot issues, CO2 is the largest contribution to the greenhouse effect of anthropogenic gas. Large-scale CO2 capture is the main way to significantly reduce greenhouse gas emissions.

[0003] Regarding CO2 capture, the mature technology at present is chemical absorption, with fast absorption, mature process, large processing capacity and other advantages, but there are high energy consumption, limited further energy saving and consumption reduction space, complex process, equipment corrosion and many other defects. Compared with chemical adsorption method, it has low energy consumption, simple process, no equipment corrosion and many other advantages. Solid adsorbent includes calcium-based adsorbent, metal organic framework (MOFs), zeolite, hypercrosslinked polymer, carbon material, alkali metal carbonate, amine-based functionalized adsorbent, etc. The polymer material prepared by emulsion template method has high porosity, certain mechanical strength, and the internal pores are three-dimensional interconnected pore structure with pore size of 0.1-300 μm. The pore size and pore size distribution can be adjusted to be appropriate and uniform. The above characteristics make the emulsion template polymer as a solid adsorbent carrier have outstanding advantages.

[0004] CN106589201A discloses a hydrophilic modification method of polystyrene material and its product, which bonds PVA to the surface of polystyrene microspheres by chloromethylating the surface of polystyrene microspheres, which can reduce the specific adsorption of biological macromolecules, and PVA contains a large number of hydroxyl groups, which is convenient for coupling specific ligands to meet the requirements of different separation modes. But the hydrophilic modification process is complex, the steps are tedious and difficult to control.

[0005] CN111825796A discloses a polyacrylate composite material for CO2 adsorption and a preparation method thereof. In the preparation process, the polymer emulsion is added to the dispersion phase, dispersed into balls at a certain speed, and then the reducing agent is added after stabilization. After solidification, drying and separation, spherical porous polyacrylate beads are prepared. After amine grafting and epoxy resin surface capping treatment, a polyacrylate composite material for CO2 adsorption is obtained.

[0006] CN114213581A discloses a preparation method of hydrophilic polyacrylate crosslinked microspheres. In this method, hydrophilic substances are connected to the comonomer by chemical bonding, and then copolymerization occurs with crosslinking agent in water phase containing stabilizer to form polymer microspheres.

[0007] The above methods all use emulsion suspension polymerization to prepare polyacrylate microspheres. Although the suspension polymerization method has been widely used in industry, the particle size of the microspheres prepared thereby mainly depends on the stirring speed during polymerization, so the particle size distribution range is wide and can only be controlled within a narrow range, and there is the problem of low yield. In addition, polyacrylate microspheres can also be prepared by precipitation polymerization in the prior art, but the production efficiency of the precipitation polymerization method is very low and does not have the prospect of industrial large-scale production.

[0008] Therefore, it has become a technical problem to be solved in the art to provide a novel polyacrylate microsphere material (polyacrylate cross-linked porous microsphere material) and a drop ball forming method and application thereof, and a fluidized bed CO2 adsorbent. SUMMARY

[0009] In order to solve the above-mentioned shortcomings and deficiencies, one object of the present application is to provide a drop ball forming method of a polyacrylate microsphere material.

[0010] Another object of the present application is also to provide a polyacrylate microsphere material prepared by the above-mentioned drop ball forming method of a polyacrylate microsphere material.

[0011] Still another object of the present application is also to provide the above-mentioned polyacrylate microsphere material as a solid adsorbent carrier for fluidized bed CO2 adsorption.

[0012] Still another object of the present application is also to provide a fluidized bed CO2 solid adsorbent, wherein the solid adsorbent carrier is the above-mentioned polyacrylate microsphere material.

[0013] In order to achieve the above objects, on the one hand, the present application provides a drop ball forming method of a polyacrylate microsphere material, wherein the drop ball forming method of the polyacrylate microsphere material comprises:

[0014] Step one: first, two or three organic monomers are added to an organic dispersed phase, and then an emulsifier, an initiator and a co-emulsifier are sequentially added to form a uniform organic phase;

[0015] Step two: deionized water is added dropwise to the organic phase for sufficient emulsification, and then a reducing agent is added to obtain a forming emulsion;

[0016] Step three: the forming emulsion is subjected to drop ball forming and aging by using a drop ball forming device, and then the microspheres after aging are dried to obtain the polyacrylate microsphere material.

[0017] As a specific embodiment of the above-mentioned droplet forming method of the present application, the organic monomer includes two or three kinds of organic monomers selected from the group consisting of glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, styrene, ethylene glycol dimethacrylate, t-butyl acrylate, t-butyl methacrylate, and trimethylolpropane triacrylate.

[0018] As a specific embodiment of the above-mentioned droplet forming method of the present application, the organic monomer includes t-butyl acrylate, t-butyl methacrylate, and trimethylolpropane triacrylate in a mass ratio of 2-3.5:0.5-1.5:2-3.5.

[0019] In the present application, the amount of the organic dispersed phase affects the yield, dispersity, and mechanical strength of the polyacrylate microspheres finally prepared. As for the volume fraction of the organic dispersed phase, it is only required to ensure that the organic monomers are fully dissolved and dispersed. As a specific embodiment of the above-mentioned droplet forming method of the present application, the volume fraction of the organic dispersed phase is 40-60% based on the total volume of the organic phase.

[0020] As a specific embodiment of the above-mentioned droplet forming method of the present application, the organic dispersed phase includes one or a combination of several kinds selected from the group consisting of cyclohexane, toluene, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, ethyl acetate, and the like; preferably, one or a combination of several kinds selected from the group consisting of toluene, cyclohexane, ethyl acetate, and the like.

[0021] As a specific embodiment of the above-mentioned droplet forming method of the present application, the amounts of the emulsifier, the initiator, and the co-emulsifier are 5-20%, 1-10%, and 1-5%, respectively, based on the total weight of the two or three kinds of organic monomers.

[0022] As a specific embodiment of the above-mentioned droplet forming method of the present application, the emulsifier includes one or a combination of several kinds selected from the group consisting of span 80, span 60, span 20, polyoxyethylene-polyoxypropylene-polyoxyethylene tri-block copolymer, and the like; preferably, polyoxyethylene-polyoxypropylene-polyoxyethylene tri-block copolymer (P123).

[0023] As a specific embodiment of the above-mentioned droplet forming method of the present application, the initiator includes one or a combination of several kinds selected from the group consisting of ammonium persulfate, potassium persulfate, benzoyl peroxide, dicumyl peroxide, t-butyl peroxide, azobis isobutyronitrile, azobis isopentyl cyanide, and the like; preferably, benzoyl peroxide.

[0024] As a specific embodiment of the above-mentioned drop ball forming method of the present application, in step one, the uniform organic phase can be formed by ultrasonic, and the present application does not make specific requirements on the time of ultrasonic, which can be reasonably adjusted according to the actual operation on site. For example, in some embodiments of the present application, the time of ultrasonic can be 5-10 min.

[0025] As a specific embodiment of the above-mentioned drop ball forming method of the present application, the co-emulsifier includes one or a combination of several of cetyl alcohol, hexanol, octanol, p-nonyl phenol, etc., and is preferably cetyl alcohol.

[0026] As a specific embodiment of the above-mentioned drop ball forming method of the present application, deionized water is added into the organic phase for sufficient emulsification according to 45-65% of the total volume of the emulsion obtained after sufficient emulsification.

[0027] As a specific embodiment of the above-mentioned drop ball forming method of the present application, in step two, after the deionized water is added into the organic phase for sufficient emulsification, the reducing agent is added, which specifically includes:

[0028] Under the stirring condition of a high-speed stirrer at a rotation speed of 1000-3000 r / min, the deionized water, i.e., the water phase, is added into the organic phase, after the addition is completed, the rotation speed is increased to 5000-10000 r / min for stirring for 5-10 min for sufficient emulsification, and then the reducing agent is added into the emulsion obtained after sufficient emulsification and continues to be stirred for 1-2 min.

[0029] As a specific embodiment of the above-mentioned drop ball forming method of the present application, the amount of the reducing agent is 5-20% based on 100% of the total weight of the two or three organic monomers.

[0030] As a specific embodiment of the above-mentioned drop ball forming method of the present application, the reducing agent includes one or a combination of several of N,N-dimethylaniline, N,N,N,N-tetramethylethylenediamine, ferrous sulfate, sodium sulfite, etc., and is preferably N,N-dimethylaniline.

[0031] As a specific embodiment of the above-mentioned drop ball forming method of the present application, in order to delay the occurrence of polymerization before forming, the preparation of the emulsion must be carried out under low-temperature conditions, i.e., the whole process of step two is carried out in a low-temperature environment, so that the temperature of the forming emulsion is reduced to below 5°C; preferably, the whole process of step one and step two is carried out in a low-temperature environment, so that the temperature of the forming emulsion is reduced to below 5°C.

[0032] As a specific embodiment of the above-mentioned droplet forming method of the present application, the droplet forming device comprises a forming emulsion storage tank, a peristaltic pump and a forming column, the forming column is a jacketed glass tube with open upper and lower ends, a mechanical stirring device is arranged at the upper end opening of the jacketed glass tube, a stirring paddle is arranged in the mechanical stirring device, an embedded droplet plate is sealingly arranged at the lower end opening of the jacketed glass tube, and the embedded droplet plate is provided with a plurality of droplet forming needles capable of extending into the forming column.

[0033] The outlet of the forming emulsion storage tank is connected to the inlet of the embedded droplet plate through a pipeline via the peristaltic pump.

[0034] As a specific embodiment of the above-mentioned droplet forming method of the present application, the lower end opening of the jacketed glass tube is "clamped" together with the embedded droplet plate by a flange, and rubber gaskets are arranged between the jacketed glass tube, the embedded droplet plate and the flange for blocking.

[0035] As a specific embodiment of the above-mentioned droplet forming method of the present application, the stirring paddle can be one of a three-blade paddle, a tuning fork, a double crescent, a cross, a straight line, a plate, a four-blade, an anchor and the like.

[0036] As a specific embodiment of the above-mentioned droplet forming method of the present application, the forming emulsion storage tank, the peristaltic pump, the jacketed glass tube, the embedded droplet plate, the droplet forming needles and the mechanical stirring device are all conventional equipment, which can be obtained by commercial purchase or self-made.

[0037] As a specific embodiment of the above-mentioned droplet forming method of the present application, in step three, the droplet forming and aging of the forming emulsion by the droplet forming device comprises:

[0038] A water solution of dispersant is added to the jacketed glass tube and heated to 50-80℃ by a water bath device connected by a jacket;

[0039] The forming emulsion is delivered into the embedded droplet plate by the peristaltic pump and is dropped into the jacketed glass tube by the droplet forming needles, since the density of the forming emulsion is lower than that of water, the droplets of the forming emulsion continuously float up in the jacketed glass tube, and during the floating process, the droplets of the forming emulsion form spherical shape under the surface tension of water and undergo polymerization reaction and preliminary solidification to quickly form small balls, when the preliminarily solidified small balls float to the upper part of the jacketed glass tube, they will continue to rotate and stay in the water solution of dispersant under the action of mechanical stirring and undergo sufficient polymerization reaction to ensure complete formation.

[0040] As a specific embodiment of the above-mentioned droplet forming method of the present application, the mass concentration of the water solution of dispersant is 0.3-2.0%.

[0041] As a specific embodiment of the above-mentioned droplet forming method of the present application, the dispersing agent comprises one or a combination of several of organic dispersing agents such as polyvinyl alcohol (PVA) and / or polyethylene glycol.

[0042] As a specific embodiment of the above-mentioned droplet forming method of the present application, the jacketed glass tube has a height of 1-2 m.

[0043] As a specific embodiment of the above-mentioned droplet forming method of the present application, the inner diameter of the droplet forming needle is 0.2-0.6 mm.

[0044] The present application does not make specific requirements for the dropping speed of the droplets, which can be reasonably adjusted according to the actual needs of the site operation, as long as it can form the emulsion droplets.

[0045] As a specific embodiment of the above-mentioned droplet forming method of the present application, the rotating speed of the mechanical stirring is 100-300 r / min.

[0046] As a specific embodiment of the above-mentioned droplet forming method of the present application, the drying is 40-80℃ drying for 4-8 hours. The drying is a conventional operation, which can be performed in an oven.

[0047] In another aspect, the present application also provides a polyacrylate microsphere material, wherein the polyacrylate microsphere material is prepared by the above-mentioned droplet forming method of the polyacrylate microsphere material.

[0048] As a specific embodiment of the above-mentioned polyacrylate microsphere material of the present application, the particle size of the polyacrylate microsphere material is 0.40-0.85 mm, and the bulk density is 0.10-0.20 g / mL.

[0049] In yet another aspect, the present application also provides the use of the above-mentioned polyacrylate microsphere material as a solid adsorbent carrier for fluidized bed CO2 adsorption.

[0050] In still another aspect, the present application also provides a fluidized bed CO2 solid adsorbent, comprising a solid adsorption carrier and an adsorption active component loaded on the surface of the solid adsorption carrier, wherein the solid adsorption carrier is the above-mentioned polyacrylate microsphere material.

[0051] The present application does not make specific requirements for the adsorption active component used in the fluidized bed CO2 solid adsorbent and its amount, which can be reasonably adjusted according to the actual needs of the site operation. For example, in some embodiments of the present application, the adsorption active component can be an organic amine such as pentaethylenehexamine.

[0052] Compared with the prior art, the present application can achieve the following beneficial technical effects:

[0053] The drop ball forming method of the polyacrylate microsphere material provided by the application first adds two or three organic monomers into an organic dispersed phase, then sequentially adds an emulsifier, an initiator and a co-emulsifier to form a uniform organic phase, subsequently drops a water phase into the organic phase for sufficient emulsification, then adds a reducing agent to obtain a water-in-oil forming emulsion with a density less than water, and finally forms the forming emulsion by using a drop ball forming method from bottom to top, to obtain the polyacrylate microsphere material by using the surface tension of the forming emulsion in water and the polymerization reaction of the forming emulsion itself.

[0054] Compared with the traditional precipitation polymerization and suspension polymerization method, the drop ball forming method of the polyacrylate microsphere material provided by the application has the following advantages:

[0055] (1) One-step ball forming, without secondary forming, and simple operation process, green and environmentally friendly, easy to industrialize, and high yield, which can be increased by more than 30% compared with the emulsion suspension polymerization method, thereby reducing the production cost;

[0056] (2) Mild operation conditions, and the polymerization forming can be performed at a low temperature without high-temperature calcination;

[0057] (3) The polyacrylate microsphere material prepared has the characteristics of low bulk density and small particle size, wherein the particle size is 0.40-0.85 mm, and the bulk density is 0.10-0.20 g / mL, which is suitable for use as a solid adsorbent carrier for fluidized bed CO2 adsorption;

[0058] (4) The polyacrylate microsphere material prepared has high sphericity, and the particle size is easy to control and has uniform particle size distribution;

[0059] (5) The polyacrylate microsphere material prepared has high mechanical strength and is not easy to be abraded during the fluidized bed operation. BRIEF DESCRIPTION OF DRAWINGS

[0060] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiment description. Obviously, the drawings in the following description are some embodiments of the application, and other drawings can also be obtained by those skilled in the art without any creative effort on the basis of these drawings.

[0061] Figure 1 It is a structure schematic diagram of the drop ball forming device used in the embodiments of the application.

[0062] Figure 2 It is a physical diagram of the polyacrylate microsphere material provided by the embodiment 2 of the application.

[0063] Figure 3The physical picture of the polyacrylate microsphere material provided for Example 5 of the present application.

[0064] Figure 4 The physical picture of the polyacrylate material provided for Comparative Example 1 of the present application.

[0065] Figure 5 The physical picture of the polyacrylate material provided for Comparative Example 5A of the present application.

[0066] Figure 6 The physical picture of the polyacrylate material provided for Comparative Example 5B of the present application.

[0067] Figure 7 The scanning electron microscope picture (500 μm) of the polyacrylate microsphere material provided for Example 1 of the present application.

[0068] Figure 8 The scanning electron microscope picture (3.00 μm) of the polyacrylate microsphere material provided for Example 1 of the present application.

[0069] Main figure number explanation:

[0070] 1. Shaped emulsion storage tank

[0071] 2. Peristaltic pump

[0072] 3. Embedded drip tray

[0073] 31. Dripping ball shaping needle

[0074] 4. Shaping column

[0075] 5. Mechanical stirring device

[0076] 51. Stirring paddle

[0077] 6. Aqueous solution of dispersant DETAILED DESCRIPTION

[0078] It is to be understood that the terminology of the specification and claims and the above listed summary of the application includes, but is not limited to, processes, methods, systems, products, or apparatuses that include, but are not limited to, the steps or units expressly identified as such.

[0079] The ranges disclosed herein are meant to include all ranges of values between the stated lower value and the stated upper value. For example, a range from 60-120 is intended to include all

[0080] In the present application, unless otherwise stated, the numerical range "a-b" means a shorthand notation for the inclusion of any integer or combination of integers between the lower value "a" and the upper value "b", wherein "a" and "b" are both integers. For example, the numerical range "0-5" means that all integers between "0-5" have been listed in the present application, and "0-5" is just a shorthand notation for these numerical combinations.

[0081] In the present application, unless otherwise stated, all embodiments and preferred embodiments mentioned in the present application can be combined with each other to form new technical solutions.

[0082] In the present application, unless otherwise stated, all technical features and preferred features mentioned in the present application can be combined with each other to form new technical solutions.

[0083] In the present application, unless otherwise stated, the term "two" used in the present application means "at least two".

[0084] In the present application, unless otherwise stated, all steps mentioned in the present application can be performed in sequence or randomly, but preferably in sequence. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, the method further comprises step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0085] In order to make the purposes, technical solutions and advantages of the present application clearer, the present application will be further described in detail below in combination with the accompanying tables, drawings and examples. The examples described below are part of the examples of the present application, rather than all the examples, and are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. Based on the examples in the present application, all other examples obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0086] Example 1

[0087] The present example provides a kind of polyacrylate microspheres material, which is prepared by drop ball forming method comprising the following specific steps:

[0088] Step one: weigh 10g tert-butyl acrylate, 2.5g tert-butyl methacrylate and 10g trimethylolpropane triacrylate into 40% of the total volume of toluene, then sequentially add 1.2g P123, 0.3g benzoyl peroxide (BPO) and 0.3g hexadecanol, and then ultrasonic in an ultrasonic cleaner for 5min to make it dissolve and mix uniformly to obtain a uniform organic phase;

[0089] Step two: weigh a certain amount of deionized water (45% of the total volume of the emulsion obtained by sufficient emulsification) as the water phase, and place the dissolved oil phase, i.e. the uniform organic phase, in an ice bath. Under the rotation speed of 1000r / min of a high-speed stirrer, slowly add the water phase to the oil phase, and after the drop is completed, increase the rotation speed to 9000r / min and stir for 5min to fully emulsify. Then add 1.2g reducing agent N,N-dimethylaniline and continue to stir for 2min to obtain a shaped emulsion;

[0090] Step three: use a drop ball forming device to perform drop ball forming and aging on the shaped emulsion, wherein the structural diagram of the drop ball forming device is as shown in Figure 1 From Figure 1 It can be seen from the above that the drop ball forming device comprises a shaped emulsion storage tank 1, a peristaltic pump 2 and a shaped column 4 with a height of 1.3m. The shaped column 4 is a jacketed glass tube with openings at the upper and lower ends. A mechanical stirring device 5 is arranged at the upper end opening of the jacketed glass tube, and a three-blade paddle stirring paddle 51 is arranged in the mechanical stirring device 5. An embedded drip tray 3 is sealingly arranged at the lower end opening of the jacketed glass tube, and the embedded drip tray 3 is provided with a plurality of drop ball forming needles 31 that can extend into the shaped column 4.

[0091] The outlet of the shaped emulsion storage tank 1 is connected to the inlet of the embedded drip tray 3 through a pipeline via the peristaltic pump 2;

[0092] Thus, the forming emulsion is drop-sphere formed and aged by the drop-sphere forming device as shown above, specifically including:

[0093] A water solution of dispersant 6, which is a water solution of polyvinyl alcohol (PVA) with a mass concentration of 0.5% in this embodiment, is prepared and added to the jacketed glass tube and mechanical stirring device 5, while ensuring that the three-blade stirring paddle 51 is below the liquid level of the water solution of polyvinyl alcohol (PVA), and then heated to 60°C by the jacketed water bath device;

[0094] The forming emulsion is delivered to the embedded drop plate by a peristaltic pump and dropped into the jacketed glass tube by a drop-sphere forming needle (with an inner diameter of 0.21 mm), and the forming emulsion droplets in the jacketed glass tube continuously float upwards, during which the forming emulsion droplets form spherical shapes under the surface tension of water and undergo polymerization and preliminary solidification. When the preliminarily solidified small spheres float to the upper part of the jacketed glass tube and approach the liquid level of the water solution of polyvinyl alcohol (PVA), they will continue to rotate and stay in the water solution of polyvinyl alcohol under the mechanical stirring (at a speed of 150 r / min) of the three-blade stirring paddle 51 and undergo sufficient polymerization to ensure complete formation.

[0095] After the formation is completed, the small spheres are taken out and dried in an oven at 50°C for 8 hours to prepare the polymer small spheres, i.e., the polyacrylate microsphere material.

[0096] Example 2

[0097] This embodiment provides a polyacrylate microsphere material prepared by a drop-sphere forming method including the following specific steps:

[0098] Step one: 10 g of tert-butyl acrylate, 7.5 g of tert-butyl methacrylate, and 10 g of trimethylolpropane triacrylate are weighed into 45% of the total volume of toluene as the organic phase, followed by the addition of 2.7 g of span 80, 0.5 g of ammonium persulfate, and 0.5 g of hexanol, and then ultrasonic cleaning for 8 min in an ultrasonic cleaning machine to dissolve and mix uniformly, obtaining a uniform organic phase;

[0099] Step two: a certain amount of deionized water (50% of the total volume of the obtained emulsion after sufficient emulsification) is weighed as the water phase, and the dissolved oil phase, i.e., the uniform organic phase, is placed in an ice bath. Under the speed of 2000 r / min of the high-speed stirrer, the water phase is slowly added to the oil phase, and after the addition is completed, the speed is increased to 8000 r / min and stirred for 6 min for sufficient emulsification, followed by the addition of 2.7 g of reducing agent N,N,N,N-tetramethyl ethylenediamine, and then stirred for 2 min to obtain the forming emulsion;

[0100] Step three: using a drop ball forming device to form and age the forming emulsion, wherein a structural schematic diagram of the drop ball forming device is as shown in Figure 1 As can be seen from Figure 1 The drop ball forming device comprises a forming emulsion storage tank 1, a peristaltic pump 2, and a forming column 4 with a height of 1.3 m, the forming column 4 being a jacketed glass tube with openings at the upper and lower ends, a mechanical stirring device 5 is arranged at the upper end opening of the jacketed glass tube, a tuning fork type stirring paddle 51 is arranged in the mechanical stirring device 5, and an embedded drop plate 3 is sealingly arranged at the lower end opening of the jacketed glass tube, the embedded drop plate 3 is provided with a plurality of drop ball forming needles 31 capable of extending into the forming column 4;

[0101] The outlet of the forming emulsion storage tank 1 is connected to the inlet of the embedded drop plate 3 through a pipeline via the peristaltic pump 2;

[0102] Therefore, the drop ball forming device as shown above is used to form and age the forming emulsion, specifically including:

[0103] A water solution 6 of a dispersing agent is prepared, which is a water solution of polyethylene glycol with a mass concentration of 1.0% in this embodiment, and is added into the jacketed glass tube and the mechanical stirring device 5, while ensuring that the tuning fork type stirring paddle 51 is below the liquid level of the water solution of polyethylene glycol, and then heated to 65℃ by a jacketed water bath device;

[0104] The forming emulsion is transported into the embedded drop plate by the peristaltic pump, and the forming emulsion is dropped into the jacketed glass tube through the drop ball forming needles (with an inner diameter of 0.31 mm), the forming emulsion droplets continuously float upwards in the jacketed glass tube, and the forming emulsion droplets form spherical shapes and undergo polymerization and preliminary solidification under the surface tension of water in the floating process, when the preliminarily solidified small balls float to the upper part of the jacketed glass tube and approach the liquid level of the water solution of polyethylene glycol, the tuning fork type stirring paddle 51 is mechanically stirred (at a speed of 250 r / min) to make the small balls continue to rotate and stay in the water solution of polyethylene glycol and fully polymerize to ensure complete forming;

[0105] After the forming is completed, the small balls are taken out and dried in an oven at 60℃ for 7 hours to prepare polymer small balls, i.e., the polyacrylate microsphere material.

[0106] Example 3

[0107] The polyacrylate microsphere material is prepared by a drop ball forming method comprising the following specific steps:

[0108] Step one: take 10g of tert-butyl acrylate, 5g of tert-butyl methacrylate and 15g of trimethylolpropane triacrylate into 50% of toluene by total volume of organic phase, then add 3.6g of span60, 1.5g of dicumyl peroxide and 0.9g of octanol in sequence, and then ultrasonic in the ultrasonic cleaning machine for 7min to make it dissolved and mixed uniformly to obtain a uniform organic phase;

[0109] Step two: take a certain amount of deionized water (55% of the total volume of the emulsion obtained after complete emulsification) as the water phase, and then place the dissolved oil phase, i.e. the organic phase, in an ice bath, and then slowly add the water phase into the oil phase in the high-speed stirring machine at a speed of 2500r / min, and then increase the speed to 7500r / min after the addition is completed and stir for 7min to complete the emulsification, and then add 3.6g of reducing agent ferrous sulfate, and then continue to stir for 1min to obtain a shaped emulsion;

[0110] Step three: use a drop ball shaping device to shape and age the shaped emulsion, wherein the structural diagram of the drop ball shaping device is as shown in Figure 1 From Figure 1 it can be seen that the drop ball shaping device comprises a shaped emulsion storage tank 1, a peristaltic pump 2 and a shaped column 4 with a height of 1.3m, the shaped column 4 is a jacketed glass tube with openings at the upper and lower ends, a mechanical stirring device 5 is arranged at the upper end opening of the jacketed glass tube, a double crescent stirring paddle 51 is arranged in the mechanical stirring device 5, an embedded drip tray 3 is sealingly arranged at the lower end opening of the jacketed glass tube, and the embedded drip tray 3 is provided with a plurality of drop ball shaping needles 31 which can extend into the shaped column 4;

[0111] The outlet of the shaped emulsion storage tank 1 is connected to the inlet of the embedded drip tray 3 through a pipeline via the peristaltic pump 2;

[0112] Therefore, the drop ball shaping device as shown above is used to shape and age the shaped emulsion, which specifically comprises:

[0113] Prepare a water solution 6 of dispersant, which is a mixed water solution of polyvinyl alcohol and polyethylene glycol with a mass concentration of 1.5% in this embodiment, and add it into the jacketed glass tube and the mechanical stirring device 5, while ensuring that the double crescent stirring paddle 51 is below the liquid level of the mixed water solution of polyvinyl alcohol and polyethylene glycol, and then heat to 70℃ through the jacketed water bath equipment;

[0114] The shaped emulsion is delivered into the embedded drop tray by a peristaltic pump and is dropped into the jacketed glass tube by a drop ball shaping needle (inner diameter of 0.41 mm). The shaped emulsion droplet continuously floats in the jacketed glass tube. During the floating process, the shaped emulsion droplet forms a spherical shape under the surface tension of water and undergoes polymerization and preliminary solidification. After the preliminary solidification, the small ball floats to the upper part of the jacketed glass tube and approaches the liquid level of the mixed aqueous solution of polyvinyl alcohol and polyethylene glycol. Under the mechanical stirring (speed of 100 r / min) of the double crescent stirring paddle 51, the small ball continues to rotate and stay in the aqueous solution of polyvinyl alcohol and polyethylene glycol and undergoes sufficient polymerization to ensure complete shaping.

[0115] After the shaping is completed, the small ball is taken out and dried in an oven at 70°C for 6 hours to prepare a polymer small ball, i.e., the polyacrylate microsphere material.

[0116] Example 4

[0117] The present example provides a polyacrylate microsphere material prepared by a drop ball shaping method comprising the following specific steps:

[0118] Step one: 9.8 g of tert-butyl acrylate, 1.4 g of tert-butyl methacrylate and 5.7 g of trimethylolpropane triacrylate are weighed and added into a mixed solution of cyclohexane and ethyl acetate accounting for 55% of the total volume of the organic phase, followed by sequentially adding 2.6 g of span 20, 1.2 g of BPO and 0.7 g of p-nonyl phenol, and then ultrasonic cleaning for 7 min in an ultrasonic cleaner to dissolve and mix uniformly to obtain a uniform organic phase;

[0119] Step two: a certain amount of deionized water (accounting for 60% of the total volume of the emulsion obtained by sufficient emulsification) is weighed as an aqueous phase. The dissolved oil phase, i.e., the uniform organic phase, is placed in an ice bath. Under the speed of 3000 r / min of the high-speed stirrer, the aqueous phase is slowly added to the oil phase. After the drop is completed, the speed is increased to 6000 r / min and stirred for 8 min for sufficient emulsification. Then 2.6 g of reducing agent N,N-dimethylaniline is added and stirred for 1 min to obtain a shaped emulsion;

[0120] Step three: the drop ball shaping device is used for drop ball shaping and aging of the shaped emulsion. The structural diagram of the drop ball shaping device is shown in Figure 1 The shaped emulsion is delivered into the embedded drop tray by a peristaltic pump and is dropped into the jacketed glass tube by a drop ball shaping needle (inner diameter of 0.41 mm). The shaped emulsion droplet continuously floats in the jacketed glass tube. During the floating process, the shaped emulsion droplet forms a spherical shape under the surface tension of water and undergoes polymerization and preliminary solidification. After the preliminary solidification, the small ball floats to the upper part of the jacketed glass tube and approaches the liquid level of the mixed aqueous solution of polyvinyl alcohol and polyethylene glycol. Under the mechanical stirring (speed of 100 r / min) of the double crescent stirring paddle 51, the small ball continues to rotate and stay in the aqueous solution of polyvinyl alcohol and polyethylene glycol and undergoes sufficient polymerization to ensure complete shaping. Figure 1As can be seen, the drop ball forming device comprises a forming emulsion storage tank 1, a peristaltic pump 2 and a forming column 4 with a height of 1.7 m, the forming column 4 being a jacketed glass tube with openings at the upper and lower ends, a mechanical stirring device 5 is arranged at the upper end opening of the jacketed glass tube, a double crescent stirring paddle 51 is arranged in the mechanical stirring device 5, and an embedded drip tray 3 is sealingly arranged at the lower end opening of the jacketed glass tube, the embedded drip tray 3 is provided with a plurality of drop ball forming needles 31 capable of extending into the forming column 4;

[0121] The outlet of the forming emulsion storage tank 1 is connected to the inlet of the embedded drip tray 3 through a pipeline via the peristaltic pump 2;

[0122] Therefore, the drop ball forming device as shown above is used to perform drop ball forming and aging on the forming emulsion, specifically including:

[0123] A water solution 6 of a dispersing agent is prepared, which is a water solution of polyvinyl alcohol (PVA) with a mass concentration of 1.5% in this embodiment, and is added into the jacketed glass tube and the mechanical stirring device 5, while ensuring that the double crescent stirring paddle 51 is located below the liquid level of the water solution of polyvinyl alcohol (PVA), and then heated to 70℃ by a jacketed water bath device;

[0124] The forming emulsion is delivered into the embedded drip tray by the peristaltic pump and is dropped into the jacketed glass tube by the drop ball forming needles (with an inner diameter of 0.51 mm), and the forming emulsion droplets continuously float upwards in the jacketed glass tube, and form spherical shapes and undergo polymerization and preliminary solidification under the surface tension of the forming emulsion droplets in water during the floating process, and when the preliminarily solidified small balls float to the upper part of the jacketed glass tube and approach the liquid level position of the water solution of polyvinyl alcohol (PVA), they will continue to rotate and stay in the water solution of polyvinyl alcohol under the mechanical stirring (at a speed of 200 r / min) of the double crescent stirring paddle 51 and perform sufficient polymerization to ensure complete forming;

[0125] After the forming is completed, the small balls are taken out and dried in an oven at 70℃ for 6 hours to prepare polymer small balls, i.e., the polyacrylate microsphere material.

[0126] Example 5

[0127] The polyacrylate microsphere material is prepared by a drop ball forming method comprising the following specific steps:

[0128] Step one: take 10 g of tert-butyl acrylate, 4.3 g of tert-butyl methacrylate and 10 g of trimethylolpropane triacrylate into a mixture of cyclohexane and ethyl acetate, which accounts for 60% of the total volume of the organic phase, then add 2.8 g of P123 and 2.0 g of span80 to form a combined emulsifier, 2.4 g of BPO and 0.7 g of cetyl alcohol and 0.5 g of hexanol to form a combined co-emulsifier, then ultrasonic in the ultrasonic cleaner for 10 min to make it dissolve and mix uniformly, and get a uniform organic phase;

[0129] Step two: take a certain amount of deionized water (65% of the total volume of the emulsion obtained by sufficient emulsification) as the water phase, and place the dissolved oil phase, i.e. the uniform organic phase, in an ice bath, under the speed of 3000 r / min of the high-speed stirrer, slowly drop the water phase into the oil phase, after dropping, increase the speed to 5000 r / min and stir for 10 min to emulsify fully, then add 4.8 g of combined reducing agent (2.4 g of N,N,N,N-tetramethyl ethylenediamine and 2.4 g of sodium sulfite), continue to stir for 1 min to get the shaped emulsion;

[0130] Step three: use the drop ball shaping device to shape and age the shaped emulsion, wherein the structural diagram of the drop ball shaping device is as shown in Figure 1 From Figure 1 it can be seen that the drop ball shaping device comprises a shaped emulsion storage tank 1, a peristaltic pump 2 and a shaped column 4 with a height of 1.7 m, the shaped column 4 is a jacketed glass tube with openings at the upper and lower ends, a mechanical stirring device 5 is arranged at the upper end opening of the jacketed glass tube, a cross-shaped stirring paddle 51 is arranged in the mechanical stirring device 5, an embedded drip tray 3 is sealingly arranged at the lower end opening of the jacketed glass tube, and the embedded drip tray 3 is provided with a plurality of drop ball shaping needles 31 which can extend into the shaped column 4;

[0131] The outlet of the shaped emulsion storage tank 1 is connected to the inlet of the embedded drip tray 3 through a pipeline via the peristaltic pump 2;

[0132] Therefore, the drop ball shaping device as shown above is used to shape and age the shaped emulsion, which specifically includes:

[0133] Prepare an aqueous solution 6 of dispersant, which is an aqueous solution of polyethylene glycol with a mass concentration of 2.0% in this embodiment, and add it into the jacketed glass tube and the mechanical stirring device 5, while ensuring that the cross-shaped stirring paddle 51 is below the liquid level of the aqueous solution of polyethylene glycol, then heat to 80℃ through the jacketed water bath equipment;

[0134] The shaped emulsion is delivered by peristaltic pump into the embedded drop tray and is dropped into the jacketed glass tube by a drop ball shaping needle (0.6 mm in inner diameter). The shaped emulsion droplet in the jacketed glass tube keeps floating up. During the floating process, the shaped emulsion droplet forms a spherical shape under the surface tension of water and initiates polymerization and preliminary solidification. When the preliminarily solidified small ball floats to the upper part of the jacketed glass tube and approaches the liquid level of the aqueous polyethylene glycol solution, it will continue to rotate and stay in the aqueous polyethylene glycol solution under the mechanical stirring (300 r / min) of the cross-shaped stirring paddle 51 and fully polymerize to ensure complete shaping.

[0135] After the shaping is completed, the small ball is taken out and dried in an oven at 80°C for 4 hours to prepare a polymer small ball, i.e., the polyacrylate microsphere material.

[0136] Comparative Example 1

[0137] This comparative example provides a polyacrylate material, which is also prepared by a drop ball shaping method. The only difference between this comparative example and Example 1 is that:

[0138] The deionized water accounts for 30% of the total volume of the emulsion obtained by full emulsification.

[0139] Comparative Example 2

[0140] This comparative example provides a polyacrylate material, which is also prepared by a drop ball shaping method. The only difference between this comparative example and Example 2 is that:

[0141] During the preparation of the shaped emulsion, the low-temperature environment is not used, but the room temperature environment is used, i.e., the dissolved oil phase, i.e., the uniform organic phase, is not placed in an ice bath.

[0142] Comparative Example 3

[0143] This comparative example provides a polyacrylate material, which is also prepared by a drop ball shaping method. The only difference between this comparative example and Example 3 is that:

[0144] The mechanical stirring device is not installed above the shaping column.

[0145] Comparative Example 4

[0146] This comparative example provides a polyacrylate material, which is also prepared by a drop ball shaping method. The only difference between this comparative example and Example 4 is that:

[0147] The shaping liquid added in the shaping column is pure water, not an aqueous PVA solution.

[0148] Comparative Example 5A

[0149] This comparative example provides a polyacrylate material which is also prepared by the drop ball forming method, the difference between this comparative example and Example 5 is only that:

[0150] The forming column is connected with a water bath device with a jacket, but heated to 40°C.

[0151] Comparative Example 5B

[0152] This comparative example provides a polyacrylate material which is also prepared by the drop ball forming method, the difference between this comparative example and Example 5 is only that:

[0153] The forming column is connected with a water bath device with a jacket, but heated to 90°C.

[0154] Comparative Example 6

[0155] This comparative example provides a polyacrylate material which is also prepared by the drop ball forming method, the difference between this comparative example and Example 5 is only that:

[0156] Step one: weigh 10 g of tert-butyl acrylate, 2.5 g of tert-butyl methacrylate and 10 g of trimethylolpropane triacrylate, add to 40% of the total volume of toluene, then add 1.2 g of P123, 0.3 g of benzoyl peroxide (BPO) and 0.3 g of cetyl alcohol in turn, and then ultrasonic cleaning machine for 5 min to make it dissolve and mix uniformly to get a uniform organic phase;

[0157] Step two: weigh a certain amount of deionized water (45% of the total volume of the emulsion obtained by sufficient emulsification) as the water phase, and place the dissolved oil phase, i.e. the uniform organic phase, in an ice bath. Under the speed of 1000 r / min of the high-speed stirrer, slowly add the water phase to the oil phase, and then increase the speed to 9000 r / min and stir for 5 min to emulsify fully. Then add 1.2 g of reducing agent N,N-dimethylaniline and continue to stir for 2 min to obtain a forming emulsion;

[0158] Step three: measure 150 mL of water and add to a 250 mL three-necked flask, and add 0.15 g of ammonium persulfate and 1.5 mL of polyvinyl alcohol dispersant. Stir with an electric stirrer at a speed of 300 rpm and heat in a constant temperature water bath at 45°C. After 10 min of constant temperature, add the prepared forming emulsion to the above three-necked flask, which will disperse into spherical shape under the action of its own interfacial tension. Continue to stir for 10 min, then take out the small balls and dry them in an oven at 60°C for 6 hours to prepare macroporous polymer balls, i.e. polyacrylate materials.

[0159] The polyacrylate microspheres prepared in Examples 1-5 of this invention have essentially the same appearance, all being regular spherical particles. Only the appearance images of the polyacrylate microspheres prepared in Examples 2 and 5 are provided here, as shown in the figures below. Figure 2 and Figure 3 As shown.

[0160] Physical images of the polyacrylate microspheres provided in Comparative Examples 1, 5A, and 5B are shown below. Figures 4-6 As shown. From Figures 4-6 As can be seen, the polyacrylate microspheres provided by Comparative Example 1, Comparative Example 5A and Comparative Example 5B have significant differences in appearance, and most of them are ellipsoidal or irregularly shaped particles with poor sphericity.

[0161] Additionally, the scanning electron microscope image of the polyacrylate microsphere material prepared in Example 1 of this invention is shown below. Figure 7 and Figure 8 As shown. From Figure 7 and Figure 8 As can be seen, the internal details of the polyacrylate microsphere material are revealed, showing a large number of macroporous structures within it.

[0162] Furthermore, the molding effects of Examples 1-5 and Comparative Examples 1-6 of the present invention, as well as the bulk density and mechanical strength of the prepared polyacrylate microspheres or polyacrylate material samples, are shown in Table 1 below.

[0163] Table 1

[0164]

[0165] 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 all above 60%, with good molding effect and uniform particle size (the higher the yield, the more uniform the particle size), and polyacrylate microspheres with low bulk density that are suitable for fluidized bed processes can be obtained.

[0166] In Comparative Example 1, the reduced proportion of deionized water resulted in a high viscosity of the emulsion, making the emulsion droplets prone to stringing and tailing, and difficult to form spheres, with the yield dropping to 20%. This indicates that in order to ensure good molding results, the aqueous phase should not account for too little of the total volume of the emulsion.

[0167] In Comparative Example 2, the molding emulsion was not prepared in a low-temperature environment, which caused the molding emulsion to rapidly polymerize into a solid before molding, thus making it impossible to further mold. This indicates that the molding emulsion should be prepared in a low-temperature environment to prolong its polymerization time.

[0168] Comparative Example 3: No mechanical stirring device is set up above the forming column, which results in that the forming emulsion droplets cannot stay in the forming liquid, i.e. the polyvinyl alcohol aqueous solution, for a long enough time, and the forming emulsion droplets float to the surface of the forming liquid and break before solidifying, which shows that a mechanical stirring device must be set up above the forming column during the forming process of the forming emulsion droplets to ensure that the forming emulsion droplets are completely solidified in the forming liquid.

[0169] In Comparative Example 4, the forming liquid added in the forming column is pure water, and the yield is greatly reduced due to the fact that no polyvinyl alcohol dispersant is added, which shows that a certain concentration of dispersant must be added to the forming liquid to ensure that the forming emulsion droplets are successfully formed and remain well dispersed.

[0170] Comparative Examples 5A and 5B respectively investigate the suitable forming temperature range. As shown in Table 1 above, when the forming temperature is too low, the solidification speed of the forming emulsion droplets is slowed down, and the forming emulsion droplets are still in the form of liquid droplets without hardness when they rise to the mechanical stirring device, which are easily broken by the stirring paddle and the particle size is reduced. When the forming temperature is too high, part of the organic phase in the forming emulsion droplets reaches the boiling point and escapes in the form of gas, which results in poor sphericity of the final small balls, as shown in Table 1 above. Therefore, the forming temperature should be controlled in the range of 50-80℃. Figures 5-6

[0171] Comparative Example 6: The polyacrylate microsphere material sample is prepared by the traditional emulsion suspension polymerization method, and the results show that the yield is only 38%, which is increased by 42% compared with Comparative Example 6, which shows that the droplet forming method provided by the present application can effectively improve the yield of the small ball carrier and ensure good sphericity.

[0172] As can be seen from Table 1 above, the polyacrylate microsphere materials prepared in Examples 1-5 have higher mechanical strength, which can increase the mechanical strength of the polyacrylate microsphere material by more than 15% compared with the existing emulsion suspension polymerization method, and the polyacrylate microsphere material is not easy to be abraded during the operation of the fluidized bed.

[0173] Application Example

[0174] ​To further evaluate the performance of the polyacrylate microsphere material samples prepared by the examples and the comparative examples of the present application as solid adsorbent carriers for fluidized bed CO2 adsorption, in this application example, a certain amount of organic amine is loaded on the polyacrylate microsphere material samples prepared by the examples 1-5 and the comparative examples 1-6 of the present application by using physical impregnation method and the adsorption performance is evaluated. The specific loading steps are as follows: 2g of the polyacrylate microsphere material samples prepared by the examples 1-5 and the comparative examples 1-6 are weighed respectively and placed in a round-bottom flask, 15g of pentaethylenehexamine is added, and the rotary evaporation instrument is used for rotary impregnation at a temperature of 60℃ for 6h, after the impregnation is completed, a small amount of alcohol is used for washing, and then drying is carried out at a temperature of 40℃ for 10h. Finally, the CO2 adsorption capacity of the polyacrylate microsphere material samples loaded with pentaethylenehexamine is tested by using a physical adsorption instrument under the conditions of a temperature of 25℃ and a pressure of 1bar, and the specific results are shown in Table 2 below.

[0175] Table 2

[0176] Item Adsorption capacity (mmol / g) Item Adsorption capacity (mmol / g) Example 1 3.8 Comparative Example 1 1.9 Example 2 3.5 Comparative Example 2 Unshaped Example 3 3.6 Comparative Example 3 Unshaped Example 4 3.3 Comparative Example 4 1.1 Example 5 3.2 Comparative Example 5A 2.1 Comparative Example 5B 2.6 Comparative Example 6 3.1

[0177] As can be seen from the above Table 2, under the same conditions, the CO2 adsorption capacity of the polyacrylate microsphere material samples prepared by the examples of the present application as solid adsorbent carriers for fluidized bed CO2 adsorption is obviously higher than that of the polyacrylate microsphere material samples prepared in the comparative examples, which indicates that the polyacrylate microsphere material samples prepared by using the drop ball forming method provided by the present application have more excellent CO2 adsorption performance.

[0178] The above is only a specific embodiment of the present application, which cannot limit the scope of the present application, so the replacement of equivalent components or equivalent changes and modifications made within the scope of the present application should still belong to the scope covered by the present patent. In addition, the technical features in the present application can be freely combined with each other, between technical features and technical features, between technical features and technical inventions, and between technical inventions and technical inventions.

Claims

1. A method for forming droplets of polyacrylate microspheres, characterized in that, The method for forming droplets of the polyacrylate microsphere material includes: Step 1: First, add the organic monomers to the organic dispersed phase, then add the emulsifier, initiator, and co-emulsifier sequentially to form a homogeneous organic phase; wherein, the organic monomers include two or three organic monomers selected from glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, styrene, ethylene glycol dimethacrylate, tert-butyl acrylate, tert-butyl methacrylate, and trimethylolpropane triacrylate; based on the total volume of the organic phase as 100%, the volume fraction of the organic dispersed phase is 40-60%; Step 2: Deionized water is added dropwise to the organic phase for thorough emulsification, and then a reducing agent is added to obtain a molded emulsion. The deionized water is added dropwise to the organic phase for thorough emulsification at a volume of 45-65% of the total volume of the emulsion obtained after thorough emulsification. Step 2 is carried out in a low-temperature environment to reduce the temperature of the molded emulsion to below 5°C. Step 3: The emulsion is subjected to drop ball forming and aging using a drop ball forming device, and then the aged balls are dried to obtain the polyacrylate microsphere material. The droplet 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 mechanical stirring device is mounted on the upper opening of the jacketed glass tube, and a stirring paddle is installed inside the mechanical stirring device. An embedded dripping plate is sealed at the lower opening of the jacketed glass tube, and the embedded dripping plate is equipped with multiple droplet forming needles that can extend into the forming column. The outlet of the forming emulsion storage tank is connected to the inlet of the embedded dripping plate via a pipeline through the peristaltic pump. Step three, 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 and heated to 50-80℃ by connecting it to a water bath through the jacket. The molding emulsion is delivered to an embedded drip tray via a peristaltic pump and then dripped into a jacketed glass tube via a dropper forming needle. Inside the jacketed glass tube, the emulsion droplets continuously rise, forming spheres under the surface tension of the water during the rising process, undergoing polymerization and initial solidification. When the initially solidified spheres rise to the top of the jacketed glass tube, they continue to rotate and remain in the aqueous dispersant solution under mechanical stirring, undergoing a full polymerization reaction to ensure complete molding. The aqueous dispersant solution has a mass concentration of 0.3-2.0%, and the dispersant includes polyvinyl alcohol and / or polyethylene glycol.

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

5.

3. The droplet forming method according to claim 1, 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.

4. The droplet forming method according to claim 3, characterized in that, The organic dispersed phase is one or a combination of toluene, cyclohexane, and ethyl acetate.

5. The droplet forming method according to any one of claims 1-4, characterized in that, Based on the total weight of organic monomers as 100%, the amounts of emulsifier, initiator and co-emulsifier are 5-20%, 1-10% and 1-5%, respectively.

6. The droplet forming method according to claim 5, 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 5, 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 5, 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 amount of reducing agent used is 5-20% based on the total weight of the organic monomers as 100%.

10. The droplet forming method according to claim 1 or 9, characterized in that, The reducing agent includes one or a combination of several of N,N-dimethylaniline, N,N,N,N-tetramethylethylenediamine, ferrous sulfate, and sodium sulfite.

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

12. The droplet forming method according to claim 1 or 11, characterized in that, The inner diameter of the drop ball forming needle is 0.2-0.6mm.

13. The droplet forming method according to claim 1 or 11, characterized in that, The mechanical stirring speed is 100-300 r / min.

14. A polyacrylate microsphere material, characterized in that, The polyacrylate microsphere material is prepared by the droplet forming method of the polyacrylate microsphere material according to any one of claims 1-13.

15. The polyacrylate microsphere material according to claim 14, characterized in that, The polyacrylate microsphere material has a particle size of 0.40-0.85 mm and a bulk density of 0.10-0.20 g / mL.

16. The use of the polyacrylate microsphere material of claim 14 or 15 as a solid adsorbent carrier for CO2 adsorption in fluidized beds.

17. A fluidized 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 microsphere material as described in claim 14 or 15.

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