Spherical amino-containing resin as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of functional resin, and particularly relates to spherical amino-containing resin as well as a preparation method and application thereof, the spherical amino-containing resin comprises a matrix white ball and an amino group connected to the matrix white ball; the matrix white ball is prepared from the following preparation raw materials: acrylonitrile, divinylbenzene and styrene in a mass ratio of 1: (0.1-0.6): (0.3-0.8); amino groups are connected to the matrix white balls through fatty amine, and the molar ratio of fatty amine to acrylonitrile in the matrix white balls is larger than or equal to 1. Through the specific ratio of the preparation raw materials, the spherical amino-containing resin has high mechanical strength, long service life and good acid gas adsorption capacity.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional resins, and particularly relates to a spherical amino-containing resin, a preparation method thereof, and an application thereof. Background Art

[0002] Since the first industrial revolution, steam power has been widely applied, and a modern energy industrial system based on fossil energy has been gradually established. This has led to a large amount of greenhouse gas emissions, especially CO2 emissions. The large amount of greenhouse gas emissions will cause global warming, and then trigger hazards such as glacier melting and sea level rise. Capturing CO2 is an effective means to inhibit greenhouse gas emissions, including post-combustion capture, pre-combustion decarbonization, oxy-fuel combustion, and chemical looping capture methods; especially post-combustion capture has received a lot of attention because of its relatively good adaptability and simple device modification. At present, post-combustion capture of CO2 includes physical adsorption method, chemical absorption method, and combined absorption method. The physical adsorption method mostly uses porous materials such as activated carbon and zeolite. Because it only relies on van der Waals force to adsorb gases, the selectivity is poor. In the chemical absorption method and the combined absorption method, amine solutions, alkali metal compound materials, membrane separation technologies, etc. are mostly used. Amine solutions are easily oxidized and degraded, resulting in reduced absorption performance, increased solution viscosity, which is not conducive to gas transmission, and poor regeneration performance, and they have a corrosive effect on equipment; alkali metal compound materials have poor regeneration performance; the materials for membrane separation technology are complex to prepare, and the pretreatment is more cumbersome, including pre-stage treatment, dehydration, and filtration. In addition, impurity particles will deposit on the membrane surface and cause blockage, and the membrane is also sensitive to sulfur-containing compounds and other trace elements, and the stability is poor. Summary of the Invention

[0003] Therefore, the purpose of the present invention is to provide a spherical amino-containing resin, a preparation method thereof, and an application thereof. The spherical amino-containing resin is simple to prepare, low in cost, high in mechanical strength, can rapidly and efficiently adsorb CO2 in a mixed gas with a low CO2 concentration, and has good long-cycle performance.

[0004] To this end, the present invention provides the following technical solutions.

[0005] The present invention provides a spherical amino-containing resin, including a matrix white ball and amino groups connected to the matrix white ball; the matrix white ball includes the following preparation raw materials: acrylonitrile, divinylbenzene, and styrene with a mass ratio of 1:0.1-0.6:0.3-0.8; the amino groups are connected to the matrix white ball through fatty amines, and the molar ratio of the fatty amines to acrylonitrile in the matrix white ball is ≥1.

[0006] Optionally, the fatty amines include aliphatic polyamines and aliphatic monoamines; optionally, the aliphatic polyamines include at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0007] Optionally, the molar ratio of the fatty amine to acrylonitrile in the matrix white balls is 1-2:1; if the content of the fatty amine is too high, the adsorption performance of the obtained spherical amino-containing resin will not be further improved, which is not suitable in terms of cost.

[0008] Optionally, the specific surface area of the matrix white balls is 100-500 m 2 / g, the particle size D 50 is 0.4-0.8 mm, and the average pore diameter is 15-30 nm.

[0009] The present invention provides a method for preparing the above-mentioned spherical amino-containing resin, which includes the following steps: S1: Dissolve the dispersant in water, and then add a mixed solution of sodium chloride and methylene blue as the aqueous phase, and mix acrylonitrile, divinylbenzene, styrene, initiator, and pore-forming agent as the oil phase, mix the aqueous phase and the oil phase, and carry out suspension polymerization under stirring to obtain matrix white balls; S2: Put the matrix white balls and fatty amine into the lye, and obtain the spherical amino-containing resin through aminolysis reaction.

[0010] In the above preparation method, the polymerization reaction is carried out under stirring in S1.

[0011] The purpose of stirring is to disperse the oil phase and uniformly suspend it in the aqueous phase to facilitate obtaining matrix white balls with the target particle size. Typically and non-limitingly, the stirring rate is adjusted adaptively according to the rotor, the size of the reaction vessel, and the total mass of the oil phase and aqueous phase, and is about 100-200 rpm.

[0012] In the polymerization reaction, the chemical reaction equation for the reaction of acrylonitrile and divinylbenzene to obtain a polymer is shown in Equation ①; in the aminolysis reaction, the cyano group on the matrix white balls will react with the fatty amine to be converted into an amide. Taking diethylenetriamine as an example, the chemical reaction equation for the aminolysis reaction is shown in Equation ②, where Alkali means under alkaline conditions.

[0013]

[0014] Methylene blue is used as a water-soluble inhibitor here. It can also eliminate the dissolved oxygen in water through redox reaction to shorten the induction period of the polymerization reaction; at the same time, during the process of methylene blue eliminating the dissolved oxygen in water, it will fade from blue to colorless and can play the role of an indicator.

[0015] Optionally, in the aqueous phase, the mass ratio of water, dispersant, sodium chloride, and methylene blue is 100:0.2-1:5-10:0.0003-0.0006.

[0016] Optionally, in the oil phase, the mass ratio of acrylonitrile, divinylbenzene, and styrene is 1:0.1-0.6:0.3-0.8; the mass ratio of the total mass sum of acrylonitrile, divinylbenzene, and styrene to the initiator is 100:0.5-1; the mass ratio of the total mass sum of acrylonitrile, divinylbenzene, and styrene to the pore-forming agent is 1:0.4-1.

[0017] When calculating the mass ratio of acrylonitrile, divinylbenzene, and styrene, the mass of divinylbenzene is calculated by multiplying the used mass by the purity, while when calculating the mass of the initiator and the pore-forming agent, divinylbenzene can be directly calculated with the used mass.

[0018] Optionally, in the step S1, the volume ratio of the aqueous phase to the oil phase is 1-6:1.

[0019] Optionally, in the step S1, the temperature of the polymerization reaction is 58-90 °C, and the time is 12-16 h.

[0020] Optionally, after the polymerization reaction in the step S1, it further includes the step of removing the pore-forming agent.

[0021] Optionally, the polymerization reaction includes two-stage polymerization. The temperature of the first-stage polymerization reaction is 58-80 °C, and the time is 4-6 h. The temperature of the second-stage polymerization reaction is 85-90 °C, and the time is 8-10 h. Dividing the polymerization reaction into two stages can achieve sufficient polymerization of the matrix white balls from the outside to the inside, making the matrix white balls have better mechanical strength. Typically and non-limitingly, the first-stage polymerization reaction includes two-stage temperature-rising processes. The target temperature of the first-stage temperature rise is 58-63 °C, and the target temperature of the second-stage temperature rise is 75-80 °C; the time taken to rise from the target temperature of the first-stage temperature rise to the target temperature of the second-stage temperature rise is 0.5-2 h.

[0022] Optionally, the method for removing the pore-forming agent includes at least one of washing, distillation, and solvent extraction. Since the distillation method is convenient for recycling the pore-forming agent, distillation is preferably used as the method for removing the pore-forming agent. Typically and non-limitingly, the distillation temperature is 85-95 °C.

[0023] Optionally, in the step S2, the temperature of the aminolysis reaction is 130-160 °C, the time is 10-15 h, and the pressure is 0.3-0.7 MPa. Conducting the aminolysis reaction under high temperature and high pressure enables the reaction to proceed fully, with high raw material utilization rate and no need to use organic solvents, which is more economical in terms of cost.

[0024] Optionally, in the step S2, the molar ratio of the fatty amine to the acrylonitrile in the matrix white balls is 1-2:1.

[0025] Optionally, in the step S2, the molar ratio of the hydroxide ion in the lye to the acrylonitrile in the matrix white balls is 3-5:1.

[0026] Optionally, in S2, the mass concentration of the lye is 25% to 32%.

[0027] Optionally, the dispersant includes at least one of polyvinyl alcohol, gelatin, and sodium carboxymethyl cellulose.

[0028] Optionally, the initiator includes at least one of benzoyl peroxide and azobisisobutyronitrile.

[0029] Optionally, the pore-forming agent includes at least one of isobutanol, methyl isobutyl carbinol, gasoline, liquid paraffin, toluene, and xylene; among them, gasoline commonly refers to No. 200 gasoline.

[0030] For different pore-forming agents, different removal methods can be adaptively selected according to their boiling points and properties. For example, pore-forming agents with an azeotropic point with water are removed by distillation; high-boiling-point pore-forming agents are removed by solvent extraction, specifically by using a low-boiling-point solvent (such as methylal) to extract the high-boiling-point pore-forming agent multiple times.

[0031] Optionally, the lye includes at least one of sodium hydroxide solution and potassium hydroxide solution.

[0032] The present invention also provides the application of the above spherical amino-group-containing resin or the spherical amino-group-containing resin prepared by the above preparation method in an acidic gas capture process; optionally, the acidic gas includes carbon dioxide.

[0033] The beneficial effects of the present invention are as follows:

[0034] The spherical amino-group-containing resin provided by the present invention includes a matrix white ball and amino groups connected to the matrix white ball; the matrix white ball includes the following preparation raw materials: acrylonitrile, divinylbenzene, and styrene with a mass ratio of 1:0.1 to 0.6:0.3 to 0.8; the amino groups are connected to the matrix white ball through fatty amines, and the molar ratio of the fatty amine to acrylonitrile in the matrix white ball is ≥1. This spherical amino-group-containing resin has relatively high mechanical strength and a high covalent organic amine grafting rate, and can simultaneously perform physical adsorption and chemical adsorption on acidic gases; it can withstand working conditions with relatively high pressure, that is, when capturing acidic gases in a mixed gas with a relatively low acidic gas concentration, pressurization can be used to achieve efficient adsorption of acidic gases; and the adsorption and desorption processes are simple, and after desorption regeneration, it still has good acidic gas capture ability and can be recycled many times. The structure of divinylbenzene is simple, only containing a benzene ring and two double bonds. Using only divinylbenzene as a cross-linking agent can avoid side reactions such as hydrolysis reactions that may occur during the preparation process, thereby improving the mechanical strength of the finished spherical amino-group-containing resin. The specific ratio of the preparation raw materials enables this spherical amino-group-containing resin to have relatively high mechanical strength, a long service life, and good acidic gas adsorption ability while.

[0035] The preparation method of the above-mentioned spherical amino-group-containing resin provided by the present invention comprises the following steps: S1: Dissolve a dispersant in water, and then add a mixed solution of sodium chloride and methylene blue as the aqueous phase. Mix acrylonitrile, divinylbenzene, styrene, an initiator, and a pore-forming agent as the oil phase. Mix the aqueous phase and the oil phase, and carry out suspension polymerization under stirring to obtain a matrix white ball; S2: Put the matrix white ball and a fatty amine into an alkali solution, and obtain the spherical amino-group-containing resin through an aminolysis reaction. This preparation method uses common materials, has a simple method, low cost, and does not require a harsh reaction environment, and can be industrially produced on a large scale. Among them, the role of sodium chloride is to stabilize the system and form balls better. As an electrolyte, after adding, it can increase the interfacial tension between water and the polymerization monomer, destroy the double-layer structure, and trigger salting-out; at the same time, it can help reduce the temperature required for the polymerization reaction. The addition of methylene blue is to prevent emulsion polymerization of the monomer and the cross-linking agent in water. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0037] Figure 1 It is an image of the spherical amino-group-containing resin obtained in Example 1 of the present invention magnified 33 times;

[0038] Figure 2 It is the SEM image of the spherical amino-group-containing resin obtained in Example 1 of the present invention;

[0039] Figure 3 It is the particle size distribution curve of the spherical amino-group-containing resin obtained in Example 1 of the present invention;

[0040] Figure 4 It is the BET curve obtained by testing the spherical amino-group-containing resin obtained in Example 1 of the present invention;

[0041] Figure 5 It is the pore size distribution curve of the spherical amino-group-containing resin obtained in Example 1 of the present invention;

[0042] Figure 6 It is the infrared spectrogram obtained by detecting the spherical amino-group-containing resin obtained in Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0043] The following embodiments are provided to better understand the present invention further. It is not limited to the described best mode, and does not limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with those of other prior arts falls within the protection scope of the present invention.

[0044] For those embodiments in which specific experimental steps or conditions are not indicated, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments whose manufacturers are not indicated, they are all conventional reagent products that can be obtained through commercial purchase.

[0045] Experimental drugs:

[0046] Acrylonitrile: containing inhibitor MEHQ (p-methoxyphenol), purchased from Shanghai Macklin Biochemical Technology;

[0047] Styrene: containing 10 - 15 ppm 4-tert-butylcatechol stabilizer, purchased from Shanghai Macklin Biochemical Technology;

[0048] Benzoyl peroxide (BPO): purchased from Shanghai Macklin Biochemical Technology;

[0049] Divinylbenzene: purity 63%, purchased from Hubei Xinyuhong Biology;

[0050] Isobutanol: purchased from Tianjin Damao Chemistry;

[0051] Diethylenetriamine: purchased from Tianjin Damao Chemistry.

[0052] Example 1

[0053] This example provides a spherical amino-containing resin and its preparation method, including the following steps:

[0054] (1) Add 1.8 g of polyvinyl alcohol to a flask containing 300 g of water. After stirring until a homogeneous solution is obtained, successively add 22 g of sodium chloride and 1.3 mg of methylene blue, and mix evenly to form the aqueous phase. Mix 31.7 g of divinylbenzene (63 wt%), 18.3 g of styrene, 50 g of acrylonitrile, 1 g of benzoyl peroxide (BPO), and 50 g of isobutanol evenly to form the oil phase. Slowly add the oil phase to the flask containing the aqueous phase. The volume ratio of the oil phase to the aqueous phase is about 1:2, and stir at a rate of 100 - 200 rpm. Gradually raise the temperature of the system from room temperature to 58 °C in about 1 h, and continue to raise it to 78 °C within 1 h, with a holding time of 3 h. After the first-stage polymerization is completed, raise the temperature to 88 °C in about 30 min, with a holding time of 8 h, and the second-stage polymerization is completed; raise the temperature to 90 °C, and remove the porogen isobutanol by distillation. After the system cools down, filter the liquid in the flask by suction, wash the spheres with water, then transfer the polymer out, spin-dry the free water on its surface by centrifugation, and dry it at 75 °C for 5 h to obtain the matrix white spheres.

[0055] (2) Weigh 120 g of sodium hydroxide, dissolve it in water to prepare a solution with a mass concentration of 30%, transfer it to an autoclave, and then put 100 g of the dried matrix white spheres into the autoclave. After the matrix white spheres are completely wetted, add 128 g of diethylenetriamine and mix evenly. Close the feeding port and airtight valve of the autoclave, gradually raise the temperature of the system from room temperature to 150 °C in about 2 h, carry out the aminolysis reaction under a pressure of about 0.6 MPa, with a reaction time of 10 h, transfer out the white spheres, wash them with water to obtain the spherical amino-group-containing resin.

[0056] Example 2

[0057] This example provides a spherical amino-group-containing resin and its preparation method. The difference compared with Example 1 is only that in step (1), in the oil phase, there are 11.1 g of divinylbenzene (63 wt%), 38.9 g of styrene, 50 g of acrylonitrile, 1 g of benzoyl peroxide (BPO), and 50 g of isobutanol; in step (2), 103 g of diethylenetriamine is added to the matrix white spheres.

[0058] Example 3

[0059] This example provides a spherical amino-group-containing resin and its preparation method. The difference compared with Example 1 is only that in step (1), in the oil phase, there are 11.1 g of divinylbenzene (63 wt%), 38.9 g of styrene, 50 g of acrylonitrile, 1 g of benzoyl peroxide (BPO), and 50 g of isobutanol; in step (2), 150 g of triethylenetetramine is added to the matrix white spheres.

[0060] Example 4

[0061] This example provides a spherical amino-containing resin and its preparation method. Compared with Example 1, the only difference is that in step (2), 103 g of diethylenetriamine is added to the matrix white balls.

[0062] Example 5

[0063] This example provides a spherical amino-containing resin and its preparation method. Compared with Example 1, the only difference is that in step (2), 155 g of diethylenetriamine is added to the matrix white balls.

[0064] Example 6

[0065] This example provides a spherical amino-containing resin and its preparation method. Compared with Example 1, the only difference is that in step (1), the polymerization reaction is as follows: the temperature of the system is raised from room temperature to 58 °C in about 1 h, and then continued to be raised to 85 °C in about 1.5 h, and then kept warm for 12 h.

[0066] Example 7

[0067] This example provides a spherical amino-containing resin and its preparation method. Compared with Example 1, the only difference is that in step (1), the oil phase contains 31.7 g of divinylbenzene (63 wt%), 18.3 g of styrene, 50 g of acrylonitrile, 1 g of benzoyl peroxide (BPO), and 40 g of isobutanol.

[0068] Example 8

[0069] This example provides a spherical amino-containing resin and its preparation method. Compared with Example 1, the only difference is that in step (1), the oil phase contains 31.7 g of divinylbenzene (63 wt%), 18.3 g of styrene, 50 g of acrylonitrile, 1 g of benzoyl peroxide (BPO), and 60 g of isobutanol.

[0070] Example 9

[0071] This example provides a spherical amino-containing resin and its preparation method, including the following steps:

[0072] (1) Add 3 g of polyvinyl alcohol to a flask containing 300 g of water. After stirring until a homogeneous solution is formed, sequentially add 15 g of sodium chloride and 1.8 mg of methylene blue, and mix evenly to obtain the aqueous phase. Mix 52.9 g of divinylbenzene (63 wt%), 16.7 g of styrene, 55.6 g of acrylonitrile, 0.63 g of benzoyl peroxide (BPO), and 125 g of isobutanol evenly to obtain the oil phase. Slowly add the oil phase to the flask containing the aqueous phase. The volume ratio of the oil phase to the aqueous phase is approximately 1:1, and stir at a rate of 100 - 200 rpm. Gradually raise the temperature of the system from room temperature to 58 °C in about 1 h, and continue to raise it to 80 °C within 1 h, with a holding time of 5 h. After the first-stage polymerization is completed, raise the temperature to 85 °C in about 30 min, with a holding time of 10 h, and the second-stage polymerization is completed. Raise the temperature to 90 °C, and remove the porogen isobutanol by distillation. After the system cools down, filter the liquid in the flask by suction, wash the spheres with water, then transfer the polymer out, spin-dry the free water on its surface by centrifugation, and dry it at 75 °C for 5 h to obtain the matrix white spheres.

[0073] (2) Weigh 210 g of sodium hydroxide, dissolve it in water to prepare a solution with a mass concentration of 25%, transfer it to an autoclave, and then add 100 g of the dried matrix white spheres to the autoclave. After the matrix white spheres are completely wetted, add 173 g of diethylenetriamine and mix evenly. Close the feeding port and airtight valve of the autoclave, gradually raise the temperature of the system from room temperature to 130 °C in about 2 h, and carry out the aminolysis reaction under a pressure of about 0.4 MPa for 15 h. Transfer out the white spheres, wash them with water to obtain spherical amino-group-containing resin.

[0074] Example 10

[0075] This example provides a spherical amino-group-containing resin and its preparation method, including the following steps:

[0076] (1) Add 2.12 g of polyvinyl alcohol to a flask containing 1060 g of water. After stirring until a homogeneous solution is formed, sequentially add 106 g of sodium chloride and 3.2 mg of methylene blue, and mix evenly to obtain the aqueous phase. Mix 8.6 g of divinylbenzene (63 wt%), 43.2 g of styrene, 54 g of acrylonitrile, 1.06 g of benzoyl peroxide (BPO), and 42.3 g of isobutanol evenly to obtain the oil phase. Slowly add the oil phase to the flask containing the aqueous phase. The volume ratio of the oil phase to the aqueous phase is about 1:6, and stir at a rate of 100 - 200 rpm. Gradually heat the system from room temperature to 58 °C in about 1 h, and continue to heat to 80 °C within 1 h, with a holding time of 3 h. After the first-stage polymerization is completed, heat to 90 °C in about 30 min, with a holding time of 8 h, and the second-stage polymerization is completed. Heat to 90 °C, and remove the porogen isobutanol by distillation. After the system cools down, filter the liquid in the flask, wash the spheres with water, then transfer the polymer out, spin-dry the free water on its surface by centrifugation, and dry at 75 °C for 5 h to obtain the matrix white spheres.

[0077] (2) Weigh 113 g of sodium hydroxide, dissolve it in water to prepare a solution with a mass concentration of 32%, transfer it to an autoclave. Subsequently, put 100 g of the dried matrix white spheres into the autoclave. After the matrix white spheres are completely wetted, add 100 g of diethylenetriamine and mix evenly. Close the feeding port and airtight valve of the autoclave. Gradually heat the system from room temperature to 160 °C in about 2 h, and carry out the aminolysis reaction at a pressure of about 0.7 MPa for 10 h. Transfer out the white spheres, wash them with water to obtain the spherical amino-group-containing resin.

[0078] Example 11

[0079] This comparative example provides a spherical amino-group-containing resin and its preparation method. The difference compared with Example 2 is only that in step (2), 194 g of diethylenetriamine is added to the matrix white spheres.

[0080] Example 12

[0081] This comparative example provides a spherical amino-group-containing resin and its preparation method. The difference compared with Example 2 is only that in step (2), 291 g of diethylenetriamine is added to the matrix white spheres.

[0082] Comparative Example 1

[0083] This comparative example provides a spherical amino-group-containing resin and its preparation method. The difference compared with Example 10 is only that in step (1), the oil phase contains 6.9 g of divinylbenzene (63 wt%), 1.1 g of glycerol trimethacrylate, 43.2 g of styrene, 54 g of acrylonitrile, 1.04 g of benzoyl peroxide (BPO), and 41.6 g of isobutanol.

[0084] Comparative Example 2

[0085] This comparative example provides a spherical amino-group-containing resin and a preparation method thereof. The difference compared with Example 10 is only that in step (1), in the oil phase, there are 6.9 g of divinylbenzene (63 wt%), 44.3 g of styrene, 54 g of acrylonitrile, 1.05 g of benzoyl peroxide (BPO), and 42 g of isobutanol.

[0086] Comparative Example 3

[0087] This comparative example provides a spherical amino-group-containing resin and a preparation method thereof. The difference compared with Example 10 is only that only the processes used in step (1) are completed to obtain the matrix white balls.

[0088] Test Example 1

[0089] Take the final product obtained in Example 1 and first observe it under a stereomicroscope at a magnification of 33 times, as shown in Figure 1 , it can be seen that its overall shape is a relatively regular sphere. Then observe its SEM image, as shown in Figure 2 , it can be seen that the surface of this spherical amino-group-containing resin presents an irregular porous structure microscopically.

[0090] Refer to GB / T 5758-2023 "Determination of Particle Size, Effective Particle Size and Uniformity Coefficient of Ion Exchange Resins", and detect the particle size distribution of the spherical amino-group-containing resin obtained in Example 1. The relationship between the resin particle size and the cumulative volume percentage of the resin on the sieve can be obtained, as shown in Figure 3 , from which the D 50 of the particle size of the sample in this example is 0.695 mm.

[0091] Test Example 2

[0092] Take the final products obtained in each example and comparative example, and refer to GB / T 12598-2023 "Determination of Abrasion Resistance and Abraded Ball Rate of Plastic Ion Exchange Resins" to measure their abraded ball rates respectively. The specific results are shown in Table 1. Among them, the abraded ball rates of the final products obtained in the examples are above 85%, and most are above 90%. In particular, the abraded ball rate of the final product obtained in Example 7 is as high as 96.71%. However, the abraded ball rate of the final product obtained in Comparative Example 1 is only 77.19% due to the use of some other raw materials, and its mechanical properties are poor. This shows that the spherical amino-group-containing resin provided in the present invention has high wear resistance, compressive strength, impact resistance, and excellent mechanical properties.

[0093] Table 1 Abraded ball rate data of each final product

[0094] Sample Sphericity of the ball after grinding Example 1 95.30％ Example 2 92.52％ Example 3 93.04％ Example 4 95.88％ Example 5 94.66％ Example 6 85.58％ Example 7 96.71％ Example 8 90.33％ Example 9 88.55％ Example 10 91.88％ Example 11 93.11％ Example 12 93.08％ Comparative Example 1 77.19％ Comparative Example 2 89.05％ Comparative Example 3 93.98％

[0095] Test Example 3

[0096] Take the final products obtained in each example and comparative example, and detect the CO2 adsorption effect of the sample by thermogravimetric analysis (TGA): Take 20 mg of the dried final product in the instrument, purge with N2 until constant weight, and introduce a mixed gas of CO2 and N2 with a volume ratio of 1:99 (flow rate 100 mL / min) at 40 °C until the sample reaches constant weight. Weigh and calculate the CO2 adsorption amount at this time; after heating to 100 °C, purge with N2 until the sample reaches constant weight to complete desorption; thus, one cycle of adsorption and desorption is completed. The TGA test data of each final product are shown in Table 2.

[0097] Table 2 TGA test data of each final product in the first cycle

[0098] Sample <![CDATA[CO2 adsorption capacity (mmol / g)]]> Example 1 3.83 Example 2 2.84 Example 3 2.79 Example 4 3.34 Example 5 3.85 Example 6 3.66 Example 7 3.41 Example 8 3.87 Example 9 3.57 Example 10 2.55 Example 11 3.27 Example 12 3.31 Comparative Example 1 2.39 Comparative Example 2 2.43 Comparative Example 3 0.51

[0099] It can be seen from Tables 1 and 2 that compared with Example 10, in Comparative Example 1, trimethylacrylic glycerol ester was used as a crosslinking agent to replace part of divinylbenzene, and its carbon dioxide adsorption amount decreased to a certain extent, and the roundness rate after grinding decreased significantly, so it could not be used for a long time. Compared with Example 10, in Comparative Example 2, the dosages of divinylbenzene and styrene were not within the scope specified in the present invention. Styrene was in excess and the amount of divinylbenzene was low, and both its roundness rate after grinding and carbon dioxide adsorption amount decreased. The comprehensive performance of the final products obtained in Comparative Examples 1 and 2 was poor. In Comparative Example 3, only the process in step (1) was directly carried out, and the obtained matrix white balls were used as adsorbents, and its CO2 adsorption amount was only 0.51 mmol / g, and the effect was very poor. By comparing each example, it can be found that in Example 9, although the dosage of the pore-forming agent was high and the specific surface area was large, the amount of acrylonitrile was relatively low and the crosslinking amount was low, resulting in a relatively low final carbon dioxide adsorption amount; and due to the high crosslinking degree and the excessive proportion of the pore-forming agent, its roundness rate after grinding was low and the mechanical properties were relatively poor. In Example 10, because the crosslinking degree was low, the pore-forming agent was less, the specific surface area was small, and the crosslinking amount was low, resulting in a poor carbon dioxide adsorption effect compared with other examples.

[0100] Test Example 4

[0101] Take the final product obtained in Example 1, repeat the above adsorption and desorption operations, and continue to detect the CO2 adsorption effect of the finished product of Example 1 under multiple cycles by thermogravimetric analysis (TGA). The CO2 adsorption amount and adsorption rate data for 10 cycles are shown in Table 3. The calculation of the adsorption rate is based on the adsorption amount in the first cycle as a reference. It can be seen that the multiple-cycle stability of the product obtained in the present invention is good.

[0102] Table 3 TGA test data of the final product of Example 1 under 10 cycles

[0103] Cycle <![CDATA[CO2 adsorption capacity (mmol / g)]]> Adsorption rate The 1st cycle 3.83 100％ The 2nd cycle 3.81 99.48％ The 3rd cycle 3.80 99.22％ The 4th cycle 3.80 99.22％ The 5th cycle 3.78 98.69％ The 6th cycle 3.80 99.09％ The 7th cycle 3.78 98.69％ The 8th cycle 3.77 98.43％ The 9th cycle 3.78 98.69％ The 10th cycle 3.77 98.43％

[0104] Test Example 5

[0105] Take the final products obtained in each example and comparative example, and refer to GB / T 19587-2017 "Determination of Specific Surface Area of Solid Materials by Gas Adsorption BET Method" to detect their BET specific surface area and pore size respectively. The results are shown in Table 4. The BET curve of the finished product of Example 1 is shown in Figure 4 , and the pore size distribution of this sample is shown in Figure 5 . Among the examples, in Example 10, due to the low crosslinking degree and less pore-forming agent used, the specific surface area is small; in Example 9, due to the high dosage of pore-forming agent, its specific surface area is relatively large.

[0106] Table 4 Specific surface area and average pore size data of each final product detected by BET method

[0107] Sample <![CDATA[Specific surface area (m 2 / g)]]> Average pore diameter (nm) Example 1 364.7718 18.7752 Example 2 226.3534 25.1065 Example 3 217.5056 26.1543 Example 4 352.4163 19.2527 Example 5 369.3207 18.4801 Example 6 355.1901 19.1106 Example 7 321.2297 19.6504 Example 8 387.5370 18.4849 Example 9 416.3394 17.6309 Example 10 196.5178 26.8064 Example 11 233.4571 24.9572 Example 12 231.9537 25.1066 Comparative Example 1 188.7914 29.3516 Comparative Example 2 181.3358 27.0817 Comparative Example 3 241.5478 28.7719

[0108] Test Example 6

[0109] Take the final product obtained in Example 1 and perform infrared spectrum detection on it. The obtained infrared spectrum is shown in Figure 6 . The carbonyl stretching vibration of amide is usually in the range of 1690-1630 cm -1 region, and the characteristic absorption peak of primary amine is usually in the range of 3500-3250 cm -1 region. It can be seen from Figure 6 that the grafting of organic amine on this spherical amino-containing resin is effective.

[0110] Test Example 7

[0111] Take the final products obtained in each example and refer to GBT 5760-2000 "Determination Method for Exchange Capacity of Hydroxide Anion Exchange Resin" to measure the total exchange capacity of each resin, so as to illustrate the amount of substance of exchangeable amine in each sample per unit mass. The specific results are shown in Table 5.

[0112] Table 5 Total exchange capacity data of each final product

[0113] Sample Total exchange capacity (mmol / g) Example 1 7.47 Example 2 6.62 Example 3 6.59 Example 4 6.43 Example 5 7.51 Example 6 7.39 Example 7 7.42 Example 8 7.49 Example 9 7.05 Example 10 6.71 Example 11 7.57 Example 12 7.60

[0114] Obviously, the above examples are only illustrations for clear explanation and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A spherical amino-containing resin, characterized in that: It includes a base white ball and an amine group connected to the base white ball; The base white ball comprises the following raw materials: acrylonitrile, divinylbenzene and styrene in a mass ratio of 1:0.1-0.6:0.3-0.8; The amino groups are connected to the base white ball through the fatty amine, and the molar ratio of the fatty amine to the acrylonitrile in the base white ball is ≥1.

2. The spherical amino-containing resin according to claim 1, characterized in that: The aliphatic amine includes aliphatic polyamine and aliphatic monoamine; optionally, the aliphatic polyamine includes at least one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; And / or, the molar ratio of the fatty amine to the acrylonitrile in the base white ball is 1 to 2:

1.

3. The spherical amino-containing resin according to claim 1 or 2, characterized in that: The specific surface area of ​​the base white ball is 100 to 500 m 2 / g, particle size D 50 The pore size is 0.4-0.8 mm, and the average pore size is 15-30 nm.

4. A method for preparing a spherical amino-containing resin as claimed in any one of claims 1 to 3, characterized in that: The steps include: S1: dissolving a dispersant in water, adding a mixed solution of sodium chloride and methylene blue as a water phase, mixing acrylonitrile, divinylbenzene, styrene, an initiator and a porogen as an oil phase, mixing the water phase with the oil phase, and performing suspension polymerization under stirring to obtain a base white ball; S2: Adding base white balls and fatty amine into alkaline solution to obtain spherical amino-containing resin through aminolysis reaction.

5. The preparation method according to claim 4, characterized in that: In the aqueous phase, the mass ratio of water, dispersant, sodium chloride and methylene blue is 100:0.2-1:5-10:0.0003-0.0006; And / or, in the oil phase, the mass ratio of acrylonitrile, divinylbenzene and styrene is 1:0.1-0.6:0.3-0.8; the mass ratio of the total mass of acrylonitrile, divinylbenzene and styrene to the initiator is 100:0.5-1; the mass ratio of the total mass of acrylonitrile, divinylbenzene and styrene to the porogen is 1:0.4-1; And / or, in S1, the volume ratio of the water phase to the oil phase is 1 to 6:

1.

6. The preparation method according to claim 4 or 5, characterized in that: In S1, the polymerization reaction temperature is 58-90° C. and the reaction time is 12-16 hours; And / or, in S1, the step of removing the porogen is further included after the polymerization reaction.

7. The preparation method according to claim 6, characterized in that: The polymerization reaction includes two stages of polymerization reaction, the first stage of polymerization reaction is at a temperature of 58-80°C and a time of 4-6 hours, and the second stage of polymerization reaction is at a temperature of 85-90°C and a time of 8-10 hours; And / or, the method of removing the porogen comprises at least one of distillation, washing, and solvent extraction.

8. The preparation method according to any one of claims 4 to 7, characterized in that: In S2, the temperature of the aminolysis reaction is 130-160°C, the time is 10-15h, and the pressure is 0.3-0.7MPa; And / or, in S2, the molar ratio of the fatty amine to the acrylonitrile in the base white ball is 1 to 2:1; And / or, in S2, the molar ratio of the hydroxide in the alkali solution to the acrylonitrile in the base white ball is 3 to 5:1; And / or, in S2, the mass concentration of the alkali solution is 25% to 32%.

9. The preparation method according to any one of claims 4 to 8, characterized in that: The dispersant includes at least one of polyvinyl alcohol, gelatin, and sodium hydroxymethyl cellulose; And / or, the initiator includes at least one of dibenzoyl peroxide and azobisisobutyronitrile; and / or, the porogen includes at least one of isobutyl alcohol, methyl isobutyl carbinol, gasoline, liquid wax, toluene, and xylene; And / or, the alkali solution includes at least one of a sodium hydroxide solution and a potassium hydroxide solution.

10. Use of the spherical amine-containing resin according to claims 1 to 3 or the spherical amine-containing resin prepared by the preparation method according to any one of claims 4 to 9 in an acid gas capture process; optionally, the acid gas includes carbon dioxide.

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