Amine-ammonium type bifunctional material for integration of carbon dioxide capture and utilization and preparation method of amine-ammonium type bifunctional material

Abstract

The invention relates to an amine-ammonium type bifunctional material for carbon dioxide capture and utilization integration and a preparation method thereof. The material comprises amido, quaternary ammonium cations and halogen anions, in the preparation method, through super-crosslinking polymerization of a polyethyleneimine monomer and glycidyl ether and further selective quaternization treatment, quaternization modification is performed on primary amine and part of secondary amine groups in a super-crosslinking polymer, so that difunctional site coupling of amine groups and quaternary ammonium-halogen ion pairs is realized, and quaternization super-crosslinking polyethyleneimine is obtained. In the material obtained by the invention, the temperatures of carbon dioxide adsorption and carbon dioxide conversion by groups are matched, cyclic carbonate can be effectively prepared by integrating capture and conversion of low-concentration carbon dioxide, and the material is simple in preparation method and low in cost.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon capture and utilization, and specifically relates to an amine-ammonium dual-functional material: a preparation method of a quaternized super-crosslinked polyethyleneimine material M-PEI-X (X=Cl, Br, I) and its application in integrated carbon dioxide capture and utilization. Background Art

[0002] The preparation of cyclic carbonates by cycloaddition reaction of carbon dioxide and epoxides is an important path for the high-value conversion of carbon dioxide. Cyclic carbonates are an important green chemical and are widely used in lithium-ion batteries, pharmaceutical manufacturing and many fine chemical fields. At present, the industry mainly uses homogeneous catalysts such as halogen-containing quaternary ammonium salts, quaternary phosphonium salts, metal complexes, and ionic liquids to catalyze the reaction. However, most of these catalytic materials with halogen-containing quaternary ammonium / quaternary phosphonium groups as active sites require high-concentration carbon dioxide (more than 99.9%) as a reaction raw material. The production of high-concentration carbon dioxide requires high-energy consumption and high-cost links such as capture, compression, and transportation of flue gas or industrial tail gas carbon dioxide (mostly with a concentration of 5% to 20%). Therefore, it is of great significance to realize the direct conversion of low-concentration carbon dioxide to cyclic carbonates through an integrated capture and conversion process.

[0003] The Chinese patent document with publication number CN108592058 A discloses a catalyst (Zn 2+ -TFM), whose nitrogen-rich structure has carbon dioxide adsorption performance at low temperatures, and zinc ions can catalyze the cycloaddition reaction of epoxide and carbon dioxide. However, the effective carbon dioxide adsorption temperature of this material is 0°C, and the cycloaddition reaction temperature is 100°C. There is a problem of mismatch between carbon dioxide capture and conversion temperature, making it difficult to achieve the coupling of carbon dioxide capture and conversion processes, that is, it is impossible to achieve direct conversion of low-concentration carbon dioxide. The development of efficient, temperature-matched capture and conversion integrated dual-functional materials is very critical to achieve the direct utilization of low-concentration carbon dioxide feed gas. Summary of the invention

[0004] The purpose of the present invention is to provide an amine-ammonium type bifunctional material for integrated carbon dioxide capture and utilization and a preparation method thereof in view of the deficiencies of current technologies. The material has both an amino group (carbon dioxide adsorption) and a quaternary ammonium-halogen ion pair (catalyzing a cycloaddition reaction); in the preparation method, the primary amine and part of the secondary amine groups in the hypercrosslinked polymer are quaternized by hypercrosslinking polymerization of polyethyleneimine monomer and glycidyl ether, and further selective quaternization treatment, so as to achieve the bifunctional site coupling of the amino group and the quaternary ammonium-halogen ion pair, and obtain the quaternized hypercrosslinked polyethyleneimine M-PEI-X (X=Cl, Br, I). In the material obtained by the present invention, the temperature matching of the group adsorbing carbon dioxide and converting carbon dioxide can effectively realize the integrated capture and conversion of low-concentration carbon dioxide to prepare cyclic carbonate, and the material preparation method is simple and low-cost.

[0005] In order to achieve the above object, the present invention provides the following specific technical solutions:

[0006] An amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization, the material composition is quaternized super-crosslinked polyethyleneimine M-PEI-X (X = Cl, Br or I), the main components include amine groups, quaternary ammonium cations, and halogen anions; wherein the mass ratio of the amine groups to the material is 5-30%, the mass ratio of the quaternary ammonium cations to the material is 2-20%, and the mass ratio of the halogen anions to the material is 5-50%.

[0007] Preferably, in the "amine-ammonium" bifunctional material, the mass ratio of the amine group to the material is 10-20%, the mass ratio of the quaternary ammonium cation to the material is 5-15%, and the mass ratio of the halogen anion to the material is 10-30%. The structural feature is the "amine-ammonium" bifunctional material containing iodide ions, M-PEI-I.

[0008] The "amine-ammonium" bifunctional material structure is a hyper-crosslinked multi-level porous polymer with a transverse circular pore diameter of 1 to 10 μm, a longitudinal pore width of 5 to 10 μm and a length of 10 to 20 μm, which is conducive to the enrichment of carbon dioxide and the exposure of catalytic sites.

[0009] The preparation method of the integrated amine-ammonium bifunctional material for carbon dioxide capture and utilization, the material is specific, and the preparation method comprises the following steps:

[0010] (1) Preparation of super cross-linked polyethyleneimine M-PEI: Add epoxy cross-linking agent to polyethyleneimine solution, stir and react at room temperature for 5 to 100 minutes, then place in liquid nitrogen for rapid cooling for 10 to 200 minutes, and then freeze for 1 to 5 days. Finally, the frozen material is vacuum freeze-dried to remove the solvent to obtain a super cross-linked polyethyleneimine material, named M-PEI;

[0011] Wherein, the mass concentration of the polyethyleneimine aqueous solution is 5% to 60%, and the amount of the epoxy crosslinking agent added is 1% to 30% of the mass of the polyethyleneimine added;

[0012] (2) Preparation of quaternized super-crosslinked polyethyleneimine M-PEI-X: The prepared M-PEI is immersed in a halide solution for quaternization, and after standing at room temperature for 10 to 15 hours, it is filtered, washed, and vacuum-dried to obtain a quaternized super-crosslinked polyethyleneimine material, named M-PEI-X.

[0013] Among them, the halide is NH 4 X or KX, the mass concentration of the halide solution is 1% to 20%; X = Cl, Br or I.

[0014] The molecular weight of the polyethyleneimine in step (1) is one or more of 600, 1200, 1800, 5000, 10000, 25000, and 70000.

[0015] The epoxy crosslinking agent in step (1) is selected from one or more of ethylene glycol diglycidyl ether, 1,2-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A-diglycidyl ether, bisphenol A-(2,3-dihydroxypropyl) glycidyl ether, bisphenol A-(3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol A-di(2,3-dihydroxypropyl) glycidyl ether, bisphenol A-di(3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol A-(2,3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F-diglycidyl ether, bisphenol F-di(3-chloro-2-hydroxypropyl) glycidyl ether and bisphenol F-di(2,3-dihydroxypropyl) glycidyl ether.

[0016] The stirring reaction time at room temperature in step (1) is 5 to 50 minutes, and the rapid cooling time in liquid nitrogen is 10 to 70 minutes.

[0017] The sample freezing temperature in step (1) is -30°C to -18°C, and the storage time is 1 to 3 days.

[0018] The quaternizing agent in step (2) is selected from one or more of ammonium chloride, ammonium bromide, ammonium iodide, potassium chloride, potassium bromide, and potassium iodide; the mass concentration of the ammonium halide or potassium halide solution is 1% to 20%.

[0019] The room temperature is 30°C ± 5°C.

[0020] The application of the amine-ammonium type bifunctional material is used for the integrated bifunctional material for carbon dioxide capture and conversion, and its application for directly converting low-concentration carbon dioxide into cyclic carbonates, which specifically includes the following steps.

[0021] The obtained quaternized super-crosslinked polyethyleneimine material is placed in a reactor, and then ethylene oxide is added and the reactor is sealed, and the air inlet valve is opened to add 0.1-5MPa, low-concentration carbon dioxide gas into the reactor, and the reaction is stopped after reacting for 6-24 hours at 25°C-120°C to obtain the target product ethylene carbonate;

[0022] Wherein, 1 to 10 mL of ethylene oxide is added for every 1 g of the quaternized super-crosslinked polyethyleneimine material;

[0023] The volume concentration of low-concentration carbon dioxide is 10% to 40%.

[0024] Compared with the prior art, the principles and beneficial effects of the present invention are as follows:

[0025] 1. The M-PEI-X material prepared by the present invention has abundant amine and quaternary ammonium-halogen ion pair coupling units ("amine-ammonium" structure). In its amine-ammonium structure, the amine group has carbon dioxide adsorption performance as a carbon dioxide adsorption site; the quaternary ammonium-halogen ion pair as a carbon dioxide cycloaddition catalytic site can efficiently catalyze carbon dioxide and epoxy cycloaddition reaction. It is important that the carbon dioxide adsorption temperature and the conversion temperature match on the two sites, therefore, the desorption problem of carbon dioxide during high temperature reaction can be overcome after the low-temperature carbon dioxide adsorption present in the reported material, and the capture conversion of low-concentration carbon dioxide is effectively realized to directly prepare cyclic carbonate.

[0026] 2. The quaternized super-crosslinked polyethyleneimine M-PEI-X material prepared by the present invention can effectively capture carbon dioxide in low-concentration carbon dioxide gas within the temperature range of 25 to 120°C. At 25°C, using 15% volume fraction of CO 2 The carbon dioxide adsorption capacity of M-PEI-X of the present invention is 1.6mmol CO 2 / g cat Compared with the carbon dioxide adsorption capacity (1.0 mmol CO 2 / g cat. ) is significantly improved. And thanks to the chemical adsorption form of amine groups on carbon dioxide and the rich hydrogen bond network of the material, the M-PEI-X material of the present invention can have higher carbon dioxide adsorption performance at higher temperatures (80-120°C). 2 At 90°C, the carbon dioxide adsorption capacity is 2.2 mmol CO 2 / g cat. .

[0027] 3. Thanks to the good carbon dioxide adsorption performance and catalytic performance of M-PEI-X at higher temperatures, the temperature of carbon dioxide adsorption and cycloaddition reaction is matched, which is more conducive to the integrated coupling of capture and conversion. The quaternized super-crosslinked polyethyleneimine M-PEI-I-1 (Example 1) prepared by the present invention has a good effect on low concentration carbon dioxide (15% CO 2 ) has significantly better performance in preparing cyclic carbonate than the existing commercial catalyst (Comparative Example 3, tetrabutylammonium iodide, TBAI) and the multi-level porous polymer Zn disclosed in the patent document with publication number CN108592058A. 2+ -TFM. At 90°C, 1MPa, 15% CO 2 Under the same conditions, the ethylene carbonate yield of M-PEI-I-1 was 90% and the selectivity was 97%, which was higher than the 61% ethylene carbonate yield and 75% ethylene carbonate selectivity of TBAI in Comparative Example 3. 2+ -TFM requires higher CO 2 partial pressure (2MPa) and higher reaction temperature (100°C).

[0028] 4. The quaternized super-crosslinked polyethyleneimine M-PEI-X material prepared by the present invention has good tolerance to high water content cycloaddition reaction system. 2 Under the conditions, water of the same mass as the catalyst is introduced into the reaction system, and the ethylene carbonate yield of the M-PEI-I-1 material is increased from 90% to 95%, and the selectivity remains unchanged, still about 97% (Example 8). Comparative Example 4 has a lower tolerance to water, and the introduction of water significantly reduces the selectivity of ethylene carbonate in the product (ethylene carbonate yield is 39%, and the selectivity is reduced from 75% to 40%), and produces a large amount of by-product ethylene glycol (ethylene glycol selectivity is 58%).

[0029] 5. The present invention proposes a selective quaternization strategy for hyper-crosslinked polyethyleneimine, which can be used to prepare organic polymer materials with dual functional sites of amine and quaternary ammonium groups. The preparation method has the advantages of simple operation and easy large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 2 are SEM images of M-PEI-I-1 and M-PEI obtained in Example 1 and Comparative Example 1.

[0031] Figure 2 The skeleton infrared spectra of M-PEI-I-1, M-PEI and M-PEI-HI obtained in Example 1 and Comparative Example 1 and Comparative Example 2 are shown.

[0032] Figure 3CO is the CO of M-PEI-I-1 obtained in Example 1 2 -TGA graph. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be noted that the following examples are illustrative, not restrictive, and the scope of protection of the present invention cannot be limited by the following examples. The raw materials required in the following examples and comparative examples are all commercially available.

[0034] In this embodiment, the SEM morphology analysis of the quaternized hyper-crosslinked polyethyleneimine M-PEI-X is performed using a HITA-CHI S-4800 scanning electron microscope.

[0035] In this embodiment, the infrared spectrum of the skeleton of the quaternized hyper-crosslinked polyethyleneimine M-PEI-X is sampled and analyzed using a ThermoScientific Nicolet 6700 infrared spectrometer.

[0036] In the present embodiment, the carbon dioxide adsorption capacity of the quaternized hyper-crosslinked polyethyleneimine M-PEI-X is measured by a thermogravimetric analyzer TGAQ50.

[0037] Example 1

[0038] The preparation steps of sample M-PEI-I-1 are as follows:

[0039] The polyethyleneimine monomer with a molecular weight of 10,000 was prepared into an aqueous solution with a mass concentration of 10%. 100 g of the above solution was added to a 200 mL sample tube. After adding a rotor magnetic stirring for 5 minutes (1000 rpm), 2 mL of ethylene glycol diglycidyl ether was added. After stirring at room temperature for 15 minutes, the sample tube containing the sample solution was placed in liquid nitrogen for rapid cooling for 30 minutes, and then the rapidly cooled sample was placed in a refrigerator freezer (-18°C) for 3 days. Finally, the frozen sample was vacuum freeze-dried to remove the solvent to obtain a super-crosslinked polyethyleneimine material, M-PEI.

[0040] Take 4g of the prepared M-PEI and soak it in 200mL 1mol / L NH 4 I solution, after standing at room temperature overnight, filtering, washing, and vacuum drying at 60°C, a quaternary ammonium super-crosslinked polyethyleneimine material, M-PEI-I-1, was obtained.

[0041] The test method for carbon dioxide adsorption performance of M-PEI-I-1 is as follows:

[0042] The carbon dioxide adsorption capacity of the prepared sample was measured by thermogravimetric analysis. The specific method is as follows: 20 mg of the material to be tested is placed in a thermogravimetric crucible and then heated at 110 °C N 2The temperature was then lowered to 90 °C and the atmosphere was switched to 15% CO 2 / N 2 The carbon dioxide adsorption capacity was calculated from the mass increase percentage and was 2.2 mmol CO 2 / g cat. .

[0043] The performance evaluation method of M-PEI-I-1 is as follows:

[0044] Weigh 1 g of quaternized super-crosslinked polyethyleneimine M-PEI-I-1 and place it in a 50 mL reactor. Then add 10 mL of ethylene oxide and seal the reactor. Open the air inlet valve and add 1 MPa pressure, CO 2 The volume concentration is 15% CO 2 / N 2 . Turn on the heating and magnetic stirring, wait until the temperature of the reactor rises to 90°C, stop the reaction after 6 hours of timing reaction, and cool in an ice-water bath. Biphenyl was used as an external standard, and gas chromatography was used for quantitative analysis. The ethylene oxide conversion rate was 93%, the ethylene carbonate yield was 90%, and the selectivity was 97%.

[0045] Example 2

[0046] The preparation steps of M-PEI-I-2 refer to Example 1, except that the molecular weight of the branched polyethyleneimine used in Example 1 is changed from 10,000 to 1,800. The remaining steps are the same as Example 1, and the prepared sample is recorded as M-PEI-I-2.

[0047] The carbon dioxide adsorption performance test method of M-PEI-I-2 is similar to that of Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-I-2 sample, and the remaining steps are the same as those of Example 1. The carbon dioxide adsorption capacity is 0.8 mmol CO 2 / g cat. The performance evaluation method of M-PEI-I-2 refers to Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-I-2 sample, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 66%, the ethylene carbonate yield is 60%, and the selectivity is 91%.

[0048] Example 3

[0049] The preparation steps of M-PEI-I-3 refer to Example 1, except that the cross-linking agent used in Implementation 1 is changed from ethylene glycol diglycidyl ether to bisphenol A diglycidyl ether, and the remaining steps are the same as Example 1. The prepared sample is recorded as M-PEI-I-3.

[0050] The carbon dioxide adsorption performance test method of M-PEI-I-3 is similar to that of Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-I-3 sample, and the remaining steps are the same as those of Example 1. The carbon dioxide adsorption capacity is 1.9 mmol CO 2 / g cat. .

[0051] The performance evaluation method of M-PEI-I-3 refers to Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-I-3 sample, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 76%, the ethylene carbonate yield is 72%, and the selectivity is 95%.

[0052] Example 4

[0053] The preparation steps of M-PEI-I-4 refer to Example 1, except that the quaternary ammonium reagent used in Example 1 is changed from ammonium iodide to potassium iodide. The remaining steps are the same as Example 1, and the prepared sample is recorded as M-PEI-I-4.

[0054] The carbon dioxide adsorption performance test method of M-PEI-I-4 is similar to that of Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-I-4 sample, and the remaining steps are the same as those of Example 1. The carbon dioxide adsorption capacity is 3.2 mmol CO 2 / g cat. .

[0055] The performance evaluation method of M-PEI-I-4 refers to Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-I-4 sample, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 16%, the ethylene carbonate yield is 15%, and the selectivity is 95%.

[0056] Example 5

[0057] The performance evaluation method of M-PEI-I-1 refers to Example 1, except that the reaction time in Example 1 is changed from 6 h to 3 h, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 52%, the ethylene carbonate yield is 50%, and the selectivity is 97%.

[0058] Example 6

[0059] The performance evaluation method of M-PEI-I-1 refers to Example 1, except that the reaction pressure in Example 1 is changed from 1 MPa to 2 MPa, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 92%, the ethylene carbonate yield is 87%, and the selectivity is 95%.

[0060] Example 7

[0061] The performance evaluation method of M-PEI-I-1 refers to Example 1, except that the reaction temperature in Example 1 is changed from 90°C to 70°C, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 54%, the ethylene carbonate yield is 52%, and the selectivity is 97%.

[0062] Example 8

[0063] The performance evaluation method of M-PEI-I-1 refers to Example 1, except that 1 mL of water was added to the reactor to examine the catalytic performance of the material for water-containing carbon dioxide, and the remaining steps were the same as Example 1. The ethylene oxide conversion rate was 98%, the ethylene carbonate yield was 95%, and the selectivity was 97%. This shows that M-PEI-I-1 has good water resistance and better catalytic conversion performance for water-containing carbon dioxide, which is because the material easily forms a rich hydrogen bond network with water.

[0064] Example 9

[0065] The performance evaluation method of M-PEI-I-1 is similar to that of Example 1, except that 5 mL of water is added to the reactor to examine the catalytic performance of the material to aqueous carbon dioxide, and the remaining steps are the same as those of Example 1. The ethylene oxide conversion rate is 99%, the ethylene carbonate yield is 94%, and the selectivity is 95%.

[0066] Example 10

[0067] The performance evaluation method of M-PEI-I-1 is similar to that of Example 1, except that 10 mL of water is added to the reactor to examine the catalytic performance of the material to aqueous carbon dioxide, and the remaining steps are the same as those of Example 1. The ethylene oxide conversion rate is 99%, the ethylene carbonate yield is 89%, and the selectivity is 90%.

[0068] Comparative Example 1

[0069] Set the unquaternized sample M-PEI as comparison sample 1

[0070] The carbon dioxide adsorption performance test method of M-PEI is referred to Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI sample, and the remaining steps are the same as Example 1. The carbon dioxide adsorption capacity is 3.8 mmolCO 2 / g cat. .

[0071] The performance evaluation method of M-PEI is referred to Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI sample, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 12%, the ethylene carbonate yield is 7%, and the selectivity is 58%.

[0072] Comparative Example 2

[0073] Comparative sample 2, the preparation steps of M-PEI-HI are as follows:

[0074] The preparation steps of M-PEI-HI refer to Example 1, except that the quaternary ammonium reagent used in Example 1 is replaced by NH 4 I was changed to HI, and the remaining steps were the same as in Example 1. The prepared sample was recorded as M-PEI-HI.

[0075] The carbon dioxide adsorption performance test method of M-PEI-HI is referred to Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-HI sample, and the remaining steps are the same as Example 1. The carbon dioxide adsorption capacity is 0.1 mmol CO 2 / g cat. .

[0076] The performance evaluation method of M-PEI-HI refers to Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the M-PEI-HI sample, and the remaining steps are the same as Example 1. The ethylene oxide conversion rate is 44%, the ethylene carbonate yield is 42%, and the selectivity is 95%.

[0077] Comparative Example 3

[0078] Comparative sample 3 is a commercial catalyst tetrabutylammonium iodide (TBAI), purchased from Tianjin Yuanli Chemical Co., Ltd.

[0079] The performance evaluation method of TBAI is as described in Example 1, except that the M-PEI-I-1 sample in Example 1 is replaced by the TBAI sample, and the remaining steps are the same as those in Example 1. The ethylene oxide conversion rate is 81%, the ethylene carbonate yield is 61%, and the selectivity is 75%.

[0080] Comparative Example 4

[0081] The performance evaluation method of TBAI is as described in Example 10, except that the M-PEI-I-1 sample in Example 10 is replaced by the TBAI sample, and the remaining steps are the same as those in Example 10. The ethylene oxide conversion rate is 98%, the ethylene carbonate yield is 39%, and the selectivity is 40%.

[0082] Embodiment 11

[0083] The quaternized super cross-linked polyethyleneimine sample M-PEI-I-1 and the comparative sample M-PEI obtained in Example 1 were characterized by SEM. The results showed that all samples showed macroporous structures and uniform element distribution. The quaternized super cross-linked polyethyleneimine sample M-PEI-I-1 was taken as a representative, and its SEM image was as follows: Figure 1As shown, the SEM results of other samples tested are Figure 1 Similarly, the obtained hyper-cross-linked polymer has a rich macroporous structure and no obvious structural changes occur before and after quaternization; the distribution of various elements is uniform, proving that the prepared sample is uniformly quaternized.

[0084] Example 12

[0085] The skeleton infrared characterization of the quaternized super-crosslinked polyethyleneimine sample M-PEI-I-1 and the comparative samples M-PEI and M-PEI-HI was performed by infrared spectrometer. Figure 2 By comparing the infrared spectra of the three materials, it can be seen that for the material M-PEI-I-1 obtained after treatment with ammonium iodide, its infrared spectrum is 3480-3270cm -1 The peak at 3200-3000cm-1 is mainly due to the secondary amine group at a lower wave number. -1 The stretching vibration peaks of quaternized primary amine and secondary amine salts are shown in Figure 2. 4 As a quaternizing agent, I can selectively quaternize the primary amine groups in the hyper-crosslinked polyethyleneimine material and retain a certain number of secondary amine groups.

[0086] Embodiment 13

[0087] The carbon dioxide adsorption capacity of the quaternary ammonium super-crosslinked polyethyleneimine sample M-PEI-I-1 was characterized by thermogravimetric analysis. Figure 3 As shown in the result graph, it can be seen that the material is saturated with carbon dioxide adsorption in about 40 minutes, and the adsorption capacity is about 2.2mmol CO 2 / g cat. .

[0088] Embodiment 14

[0089] The elemental composition of the quaternized hyper-crosslinked polyethyleneimine samples M-PEI-I-1, M-PEI-I-4 and the comparative samples M-PEI and M-PEI-HI was analyzed by X-ray photoelectron spectrometry. The mass proportions of amine groups, quaternary ammonium groups and iodide ions in the prepared materials were calculated based on the molar proportions of different elements. The results are shown in Table 1.

[0090] Table 1. Composition analysis of quaternized hypercrosslinked polyethyleneimine samples

[0091]

[0092] The present invention is described above by way of example. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacement that can be made by those skilled in the art without inventive effort falls within the protection scope of the present invention.

[0093] Matters not covered by the present invention are known technologies.

Claims

1. An amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization, characterized in that: The material is composed of quaternized super-crosslinked polyethyleneimine M-PEI-X (X=Cl, Br or I), and its main components include amine groups, quaternary ammonium cations and halogen anions; wherein the mass ratio of the amine groups to the material is 5-30%, the mass ratio of the quaternary ammonium cations to the material is 2-20%, and the mass ratio of the halogen anions to the material is 5-50%.

2. The amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 1, characterized in that: In the dual-functional material, the mass ratio of amine groups to the material is 10-20%, the mass ratio of quaternary ammonium cations to the material is 5-15%, and the mass ratio of halogen anions to the material is 10-30%; X=I.

3. The amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 1, characterized in that: The dual-function material structure is a super-crosslinked multi-level porous polymer, with a transverse circular hole diameter of 1 to 10 μm, a longitudinal channel width of 5 to 10 μm, and a length of 10 to 20 μm.

4. The method for preparing the amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 1, characterized in that: The method comprises the following steps: (1) Preparation of hyper-crosslinked polyethyleneimine M-PEI: Add epoxy crosslinking agent to polyethyleneimine solution, stir and react at room temperature for 5 to 100 minutes, then place in liquid nitrogen for rapid cooling for 10 to 200 minutes, and then freeze and store for 1 to 5 days; finally, the frozen material is vacuum freeze-dried to remove the solvent to obtain a hyper-crosslinked polyethyleneimine material, named M-PEI; The mass concentration of the polyethyleneimine solution is 5% to 60%, and the amount of the epoxy crosslinking agent added is 1% to 30% of the mass of the polyethyleneimine added; The epoxy crosslinking agent is selected from one or more of ethylene glycol diglycidyl ether, 1,2-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A-diglycidyl ether, bisphenol A-(2,3-dihydroxypropyl) glycidyl ether, bisphenol A-(3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol A-di(2,3-dihydroxypropyl) glycidyl ether, bisphenol A-di(3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol A-(2,3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F-diglycidyl ether, bisphenol F-di(3-chloro-2-hydroxypropyl) glycidyl ether and bisphenol F-di(2,3-dihydroxypropyl) glycidyl ether; (2) Preparation of quaternized hyper-crosslinked polyethyleneimine M-PEI-X: The prepared M-PEI is immersed in a halide solution for quaternization, and after standing at room temperature for 10 to 15 hours, the quaternized hyper-crosslinked polyethyleneimine material is obtained by filtering, washing, and vacuum drying, and is named M-PEI-X; Wherein, the halide salt is NH4X or KX, the mass concentration of the halide salt solution is 1% to 20%; X=Cl, Br or I.

5. The method for preparing the amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 4, characterized in that: The molecular weight of the polyethyleneimine in step (1) is one or more of 600, 1200, 1800, 5000, 10000, 25000, and 70000.

6. The method for preparing the amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 4, characterized in that: The stirring reaction time at room temperature in step (1) is 5 to 50 minutes; and the rapid cooling time in liquid nitrogen is 10 to 70 minutes.

7. The method for preparing the amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 4, characterized in that: In step (1), the freezing temperature is -30°C to -18°C, and the storage time is 1 to 3 days.

8. The method for preparing the amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 4, characterized in that: The quaternizing agent in step (2) is selected from one or more of ammonium chloride, ammonium bromide, ammonium iodide, potassium chloride, potassium bromide and potassium iodide.

9. The use of the amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 1, characterized in that: Used to directly convert low-concentration carbon dioxide to prepare cyclic carbonates.

10. The use of the amine-ammonium type dual-functional material for integrated carbon dioxide capture and utilization as claimed in claim 9, characterized in that: The following steps are involved: The obtained quaternized super-crosslinked polyethyleneimine material is placed in a reactor, and then ethylene oxide is added and the reactor is sealed, and the air inlet valve is opened to add 0.1-5MPa, low-concentration carbon dioxide gas into the reactor, and the reaction is stopped after reacting for 6-24 hours at 25°C-120°C to obtain the target product ethylene carbonate; Wherein, 1 to 10 mL of ethylene oxide is added for every 1 g of the quaternized super-crosslinked polyethyleneimine material; The volume concentration of low-concentration carbon dioxide is 10% to 40%.

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