An amine-ammonium bifunctional material for carbon dioxide capture and utilization integration and a preparation method thereof

Abstract

The application discloses an amine-ammonium bifunctional material for carbon dioxide capture and utilization integration and a preparation method thereof. The material composition comprises amine groups, quaternary ammonium cations and halogen anions. In the preparation method, quaternary ammonium modification of primary amine and part of secondary amine groups in the hypercrosslinked polymer is realized by hypercrosslinking polymerization of polyethylene imine monomers and glycidyl ether and further selective quaternary ammonium treatment, so that the bifunctional site coupling of amine groups and quaternary ammonium group-halogen ion pairs is realized, and quaternary ammonium hypercrosslinked polyethylene imine is obtained. In the material obtained by the application, the temperature matching of the group adsorbing carbon dioxide and converting carbon dioxide can effectively realize the integration of low-concentration carbon dioxide capture and conversion to form cyclic carbonates, and the material preparation method is simple and low in cost.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of carbon capture and utilization, and particularly relates to a preparation method of an amine-ammonium bifunctional material, i.e., a quaternary ammonium supercrosslinked polyethyleneimine material M-PEI-X (X = Cl, Br, I), and application of the material in carbon dioxide capture and utilization integration. BACKGROUND

[0002] The cycloaddition reaction of carbon dioxide and epoxide to prepare cyclic carbonate is an important path for high-value conversion of carbon dioxide. Cyclic carbonate is an important green chemical and has a wide range of applications in lithium ion batteries, pharmaceutical manufacturing and many fine chemical industries. At present, the reaction is mainly catalyzed by homogeneous catalysts such as halogen-containing quaternary ammonium salts, quaternary phosphonium salts, metal complexes and ionic liquids. However, most of the catalyst materials with halogen-containing quaternary ammonium / phosphonium groups as active sites currently require high-concentration carbon dioxide (99.9% or more) as a raw material. The production of high-concentration carbon dioxide requires high energy consumption and high cost processes such as capture, compression and transportation from flue gas or industrial tail gas carbon dioxide (concentration is mostly between 5% and 20%). Therefore, it is of great significance to realize the direct conversion of low-concentration carbon dioxide to cyclic carbonate through the capture and conversion integration process.

[0003] Chinese patent document CN108592058 A discloses a multi-level porous polymer and zinc ion coordination catalyst (Zn 2+ -TFM) which has carbon dioxide adsorption performance at low temperature due to its nitrogen-rich structure, and the zinc ion can catalyze the cycloaddition reaction of epoxide and carbon dioxide. However, the effective carbon dioxide adsorption temperature of the material is 0℃, and the cycloaddition reaction temperature is 100℃, which has the problem of mismatching of carbon dioxide capture and conversion temperature, and it is difficult to realize the coupling of carbon dioxide capture and conversion process, i.e., the direct conversion of low-concentration carbon dioxide cannot be realized. It is very crucial to develop high-efficiency, temperature-matched capture and conversion integrated bifunctional materials for realizing the direct utilization of low-concentration carbon dioxide raw gas. SUMMARY

[0004] The present application aims at the current technical deficiencies, and provides an amine-ammonium bifunctional material for carbon dioxide capture and utilization integration and a preparation method thereof.The material has amine groups (adsorbing carbon dioxide) and quaternary ammonium halogen ion pairs (catalyzing cycloaddition reaction) at the same time; in the preparation method, through hypercrosslinked polymerization of polyethylene imine monomers and glycidyl ether, and further selective quaternary ammonium treatment for quaternary ammonium modification of primary amine and part of secondary amine groups in the hypercrosslinked polymer, the bifunctional site coupling of amine groups and quaternary ammonium halogen ion pairs is realized, and quaternary ammonium hypercrosslinked polyethylene imine M-PEI-X (X=Cl, Br, I) is obtained.The material obtained by the present application matches the temperature of group adsorbing carbon dioxide and converting carbon dioxide, and can effectively realize the capture and conversion integration of low-concentration carbon dioxide to cyclic carbonate, and the material preparation method is simple and low in cost.

[0005] In order to achieve the above-mentioned purpose, the present application provides the following specific technical solutions:

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

[0007] Preferably, in the amine-ammonium bifunctional material, the mass ratio of amine groups in the material is 10-20%, the mass ratio of quaternary ammonium cations in the material is 5%-15%, and the mass ratio of halogen anions in the material is 10%-30%. The structural feature is an amine-ammonium bifunctional material containing iodine ions, M-PEI-I.

[0008] The structure of the amine-ammonium bifunctional material is a hypercrosslinked multi-level pore polymer, the transverse circular hole diameter is 1-10 microns, the longitudinal pore width is 5-10 microns, and the length is 10-20 microns, which is beneficial to the enrichment of carbon dioxide and the exposure of catalytic sites.

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

[0010] (1) Preparation of hypercrosslinked polyethylene imine M-PEI: add an epoxy crosslinking agent to a polyethylene imine solution, stir at room temperature for 5-100 min, then rapidly cool in liquid nitrogen for 10-200 min, and then freeze for 1-5 days. Finally, the frozen material is dried by vacuum freeze drying to remove the solvent to obtain a hypercrosslinked polyethylene imine material, which is named M-PEI;

[0011] The mass concentration of the polyethyleneimine aqueous solution is 5% to 60%, and the addition amount of the epoxy crosslinking agent is 1% to 30% of the mass of the polyethyleneimine.

[0012] (2) Preparation of the quaternary ammonium supercrosslinked polyethyleneimine M-PEI-X: The prepared M-PEI is immersed in a halide salt solution for quaternization, and after standing at room temperature for 10 to 15 hours, filtration, washing, and vacuum drying, the quaternary ammonium supercrosslinked polyethyleneimine material is obtained, which is named M-PEI-X.

[0013] The halide salt is NH4X or KX, and the mass concentration of the halide salt 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 min. The liquid nitrogen quenching time is 10 to 70 min.

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

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

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

[0021] The obtained quaternary ammonium supercrosslinked polyethyleneimine material is placed in a reaction kettle, then ethylene oxide is added and the reaction kettle is sealed, 0.1-5 MPa, low-concentration carbon dioxide gas is added to the reaction kettle by opening the gas inlet valve, the reaction is stopped after 25-120 DEG C, 6-24 h, and the target product ethylene carbonate is obtained;

[0022] 1-10 mL of ethylene oxide is added per 1 g of the obtained quaternary ammonium supercrosslinked polyethyleneimine material;

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

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

[0025] 1. The M-PEI-X material prepared by the present application has abundant amine groups and quaternary ammonium group-halogen ion pair coupling units ("amine-ammonium" structure). In the amine-ammonium structure, the amine group serves as a carbon dioxide adsorption site and has carbon dioxide adsorption performance; the quaternary ammonium group-halogen ion pair serves as a carbon dioxide cycloaddition catalytic site and can efficiently catalyze the cycloaddition reaction of carbon dioxide and an epoxy group. Importantly, the carbon dioxide adsorption temperature and conversion temperature on the two sites match, so the problem of desorption of carbon dioxide when low-concentration carbon dioxide is adsorbed at low temperature and then reacted at high temperature in the reported materials can be overcome, and the direct preparation of cyclic carbonates from low-concentration carbon dioxide capture and conversion can be effectively realized.

[0026] 2. The quaternary ammonium supercrosslinked polyethyleneimine M-PEI-X material prepared by the present application can effectively capture carbon dioxide in low-concentration carbon dioxide gas in the temperature range of 25-120 DEG C. At 25 DEG C, using 15% by volume of CO2, the carbon dioxide adsorption capacity of the M-PEI-X material of the present application is 1.6 mmol CO2 / g cat , which is significantly improved compared with the carbon dioxide adsorption capacity (1.0 mmol CO2 / g cat. ) of the multi-level porous polymer disclosed in the patent document with publication number CN108592058A. And thanks to the chemical adsorption form of the amine group to carbon dioxide and the abundant hydrogen bond network of the material, the M-PEI-X material of the present application can have higher carbon dioxide adsorption performance at higher temperatures (80-120 DEG C), using 15% by volume of CO2, the carbon dioxide adsorption capacity is 2.2 mmol CO2 / g cat. at 90 DEG C.

[0027] 3, The good carbon dioxide adsorption performance of M-PEI-X at high temperature and catalytic performance make the temperature of carbon dioxide adsorption and cycloaddition reaction match, which is more conducive to the coupling of capture and conversion. The performance of the quaternary ammonium supercrosslinked polyethylene imine M-PEI-I-1 (Example 1) prepared in the application in preparing cyclic carbonates from low-concentration carbon dioxide (15% CO2) is obviously superior to that of the existing commercial catalyst (Tetrabutylammonium iodide, TBAI) in Comparative Example 3 and the multi-level porous polymer Zn 2+ -TFM. The ethylene carbonate yield of M-PEI-I-1 is 90% and the selectivity is 97% under the condition of 90℃, 1MPa, 15% CO2, which is higher than the ethylene carbonate yield of 61% and the ethylene carbonate selectivity of 75% of TBAI in Comparative Example 3. The multi-level porous polymer Zn 2+ -TFM requires a higher CO2 partial pressure (2MPa) and a higher reaction temperature (100℃).

[0028] 4, The quaternary ammonium supercrosslinked polyethylene imine M-PEI-X material prepared in the application has good tolerance to the cycloaddition reaction system with high water content. Under the condition of 90℃, 1MPa, 15% CO2, the introduction of water with the same mass as the catalyst into the reaction system increases the ethylene carbonate yield of the M-PEI-I-1 material from 90% to 95%, and the selectivity remains unchanged, still about 97% (Example 8). The tolerance of Comparative Example 4 to water is low, and the introduction of water significantly reduces the selectivity of ethylene carbonate in the product (the ethylene carbonate yield is 39%, and the selectivity decreases from 75% to 40%), and a large amount of byproduct ethylene glycol is produced (the ethylene glycol selectivity is 58%).

[0029] 5, The application provides a selective quaternization strategy for supercrosslinked polyethylene imine, which can be used to prepare an organic polymer material with bifunctional sites of amine groups and quaternary ammonium groups, and the preparation method has the advantages of simple operation and easy large-scale production. BRIEF DESCRIPTION OF DRAWINGS

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

[0031] Figure 2 Skeleton infrared spectra of M-PEI-I-1, M-PEI, and M-PEI-HI obtained in Example 1 and Comparative Examples 1, 2.

[0032] Figure 3 CO2-TGA graph of M-PEI-I-1 obtained in Example 1. DETAILED DESCRIPTION

[0033] The application will be described in further detail below with reference to the drawings and specific embodiments. It should be noted that the following examples are illustrative, and are not intended to limit the scope of the application. The raw materials required in the following examples and comparative examples are commercially available.

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

[0035] In this embodiment, the skeleton infrared spectrum of the quaternary ammonium supercrosslinked polyethyleneimine M-PEI-X is analyzed by sampling using a Thermo Scientific Nicolet 6700 infrared spectrometer.

[0036] In this embodiment, the carbon dioxide adsorption capacity of the quaternary ammonium supercrosslinked polyethyleneimine M-PEI-X is determined by a thermal gravimetric analyzer TGA Q50.

[0037] Example 1

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

[0039] A polyethyleneimine monomer with a molecular weight of 10000 is prepared into a 10% mass concentration aqueous solution, 100g of the above solution is taken into a 200mL sample tube, after adding 2mL of ethylene glycol diglycidyl ether and stirring at room temperature for 15 minutes, the sample tube containing the sample solution is placed in liquid nitrogen for rapid cooling for 30 minutes, and then the rapidly cooled sample is placed in a freezer compartment (-18℃) for storage for 3 days. Finally, the frozen sample is dried by vacuum freeze-drying to obtain a supercrosslinked polyethyleneimine material, M-PEI.

[0040] 4g of the prepared M-PEI is soaked in 200mL of 1mol / L NH4I solution, and after standing at room temperature overnight, filtration, washing, and vacuum drying at 60℃, a quaternary ammonium supercrosslinked polyethyleneimine material, M-PEI-I-1, is obtained.

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

[0042] The carbon dioxide adsorption capacity of the prepared sample is determined by a thermal gravimetric analyzer. The specific method is as follows: 20mg of the material to be tested is placed in a thermal gravimetric crucible, then pretreated at 110℃ under N2 atmosphere for 30 minutes, then the temperature is reduced to 90℃, and the atmosphere is switched to 15% CO2 / N2 for carbon dioxide adsorption. The carbon dioxide adsorption capacity is calculated by the percentage increase in mass, which is 2.2mmol CO2 / g.cat. .

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

[0044] 1 g of quaternary ammonium supercrosslinked polyethyleneimine M-PEI-I-1 was weighed into a 50 mL reaction kettle, then 10 mL of ethylene oxide was added and the reaction kettle was sealed, a CO2 / N2 with a pressure of 1 MPa and a volume concentration of CO2 of 15% was added to the reaction kettle by opening the gas inlet valve. Turn on the heating and magnetic stirring, wait for the reaction kettle temperature to rise to 90°C, stop the reaction after 6 h of timing reaction, and cool in an ice water bath. Quantitative analysis was performed using gas chromatography with biphenyl as an external standard. The conversion rate of ethylene oxide was 93%, the yield of ethylene carbonate 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 10000 to 1800, and the remaining steps are the same as in Example 1. The prepared sample is denoted as M-PEI-I-2.

[0047] The carbon dioxide adsorption performance test 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 in Example 1. The carbon dioxide adsorption capacity is 0.8 mmol CO2 / 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 in Example 1. The conversion rate of ethylene oxide is 66%, the yield of ethylene carbonate 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 crosslinking agent used in Example 1 is changed from ethylene glycol diglycidyl ether to bisphenol A-diglycidyl ether, and the remaining steps are the same as in Example 1. The prepared sample is denoted as M-PEI-I-3.

[0050] The carbon dioxide adsorption performance test 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 in Example 1. The carbon dioxide adsorption capacity is 1.9 mmol CO2 / g cat. .

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

[0052] Example 4

[0053] The preparation steps of M-PEI-I-4 were the same as those in Example 1, except that the quaternary ammonium reagent used in Example 1 was changed from ammonium iodide to potassium iodide, and the other steps were the same as those in Example 1. The prepared sample was denoted as M-PEI-I-4.

[0054] The carbon dioxide adsorption performance test method of M-PEI-I-4 was the same as that of Example 1, except that the M-PEI-I-1 sample in Example 1 was replaced by the M-PEI-I-4 sample, and the other steps were the same as those in Example 1. The carbon dioxide adsorption capacity was 3.2 mmol CO2 / g cat. .

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

[0056] Example 5

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

[0058] Example 6

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

[0060] Example 7

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

[0062] Example 8

[0063] The performance evaluation method of M-PEI-I-1 refers to Example 1, except that 1 mL of water is additionally added to the reaction kettle to investigate the catalytic performance of the material on water-containing carbon dioxide, and the remaining steps are the same as in Example 1. The conversion rate of ethylene oxide is 98%, the ethylene carbonate yield is 95%, and the selectivity is 97%. It shows that M-PEI-I-1 has good water resistance and better catalytic conversion performance on water-containing carbon dioxide, which is due to the easy formation of a rich hydrogen bond network between the material and water.

[0064] Example 9

[0065] The performance evaluation method of M-PEI-I-1 refers to Example 1, except that 1 mL of water is additionally added to the reaction kettle to investigate the catalytic performance of the material on water-containing carbon dioxide, and the remaining steps are the same as in Example 1. The conversion rate of ethylene oxide is 98%, the ethylene carbonate yield is 95%, and the selectivity is 97%. It shows that M-PEI-I-1 has good water resistance and better catalytic conversion performance on water-containing carbon dioxide, which is due to the easy formation of a rich hydrogen bond network between the material and water.

[0066] Example 10

[0067] The performance evaluation method of M-PEI-I-1 refers to Example 1, except that 1 mL of water is additionally added to the reaction kettle to investigate the catalytic performance of the material on water-containing carbon dioxide, and the remaining steps are the same as in Example 1. The conversion rate of ethylene oxide is 98%, the ethylene carbonate yield is 95%, and the selectivity is 97%. It shows that M-PEI-I-1 has good water resistance and better catalytic conversion performance on water-containing carbon dioxide, which is due to the easy formation of a rich hydrogen bond network between the material and water.

[0068] Comparative Example 1

[0069] The un-quaternized sample M-PEI is set as Comparative Sample 1

[0070] The carbon dioxide adsorption performance test method of M-PEI refers 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 in Example 1. The carbon dioxide adsorption capacity is 3.8 mmol CO2 / g cat. .

[0071] The performance evaluation method of M-PEI refers 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 in Example 1. The conversion rate of ethylene oxide 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 changed from NH4I to HI, and the remaining steps are the same as in Example 1. The prepared sample is denoted as M-PEI-HI.

[0075] The carbon dioxide adsorption performance test method of M-PEI-HI was the same as Example 1 except that the M-PEI-I-1 sample in Example 1 was replaced by the M-PEI-HI sample, and the remaining steps were the same as Example 1. The carbon dioxide adsorption capacity was 0.1 mmol CO2 / g cat. .

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

[0077] Comparative Example 3

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

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

[0080] Comparative Example 4

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

[0082] Example 11

[0083] The quaternary ammonium supercrosslinked polyethyleneimine sample M-PEI-I-1 obtained in Example 1 and the comparative sample M-PEI were characterized by SEM, and the results showed that all the samples showed macroporous structure, and the element distribution was uniform. Taking the quaternary ammonium supercrosslinked polyethyleneimine sample M-PEI-I-1 as a representative, its SEM image is shown in Figure 1 , and the SEM results of other samples to be tested were similar to Figure 1 , that is, the obtained supercrosslinked polymer had abundant macroporous structure and no obvious structural change occurred before and after quaternary ammonium, and the element distribution was uniform, proving that the prepared sample was uniformly quaternized.

[0084] Example 12

[0085] The infrared spectrometer was used for skeleton infrared characterization of quaternary ammonium supercrosslinked polyethylene imine sample M-PEI-I-1 and comparative samples M-PEI and M-PEI-HI, and the infrared spectra thereof are shown in Figure 2 As can be seen from the infrared spectra of the three materials, for the material M-PEI-I-1 obtained after treatment with ammonium iodide, the peaks at 3480-3270 cm -1 mainly represent the lower wavenumber secondary amine groups, and then the stretching vibration peaks of quaternary ammonium primary amine and secondary amine salt at 3200-3000 cm -1 The above results show that the use of NH4I as a quaternary ammonium reagent can selectively quaternize the primary amine groups in the supercrosslinked polyethylene imine material and retain a certain number of secondary amine groups.

[0086] Example 13

[0087] The carbon dioxide adsorption capacity of the quaternary ammonium supercrosslinked polyethylene imine sample M-PEI-I-1 was characterized by a thermal gravimetric analyzer, and the results are shown in Figure 3 As can be seen from the results, the material is saturated with carbon dioxide adsorption at about 40 min, and the adsorption capacity is about 2.2 mmol CO2 / g cat. .

[0088] Example 14

[0089] The X-ray photoelectron spectrometer was used for element composition analysis of the quaternary ammonium supercrosslinked polyethylene imine samples M-PEI-I-1 and M-PEI-I-4 and comparative samples M-PEI and M-PEI-HI, and the mass proportions of amine groups, quaternary ammonium groups and iodine ions in the prepared materials were calculated based on the molar proportions of different elements, and the results are shown in Table 1.

[0090] Table 1, composition analysis of quaternary ammonium supercrosslinked polyethylene imine samples

[0091]

[0092] The above exemplary description of the present application should be noted that without departing from the core of the present application, any simple modification, modification or other equivalent replacement which can not cost creative labor of those skilled in the art falls within the protection scope of the present application.

[0093] The remaining matters of the present application are well-known technologies.

Claims

1. An amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization, characterized in that, The material is composed of quaternized supercrosslinked polyethyleneimine M-PEI-X, and its main components include amino groups, quaternary ammonium cations, and halide anions. Among them, the amino groups account for 5-30% of the material by mass, the quaternary ammonium cations account for 2-20% of the material by mass, and the halide anions account for 5-50% of the material by mass. The preparation method of the amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization includes the following steps: (1) Preparation of hypercrosslinked polyethyleneimine M-PEI: Add epoxy crosslinking agent to polyethyleneimine solution, stir at room temperature for 5~100 min, then place in liquid nitrogen for rapid cooling for 10~200 min, then freeze for 1~5 days; finally, use vacuum freeze-drying to remove solvent to obtain hypercrosslinked polyethyleneimine material, named M-PEI; The polyethyleneimine solution has a mass concentration of 5% to 60%, and the epoxy crosslinking agent is added at a mass of 1% to 30% of the polyethyleneimine. (2) Preparation of quaternized supercrosslinked polyethyleneimine M-PEI-X: The prepared M-PEI was immersed in a halide salt solution for quaternization. After standing at room temperature for 10 to 15 hours, it was filtered, washed, and vacuum dried to obtain the quaternized supercrosslinked polyethyleneimine material, named M-PEI-X. The halide is NH4X or KX, and the mass concentration of the halide solution is 1%~20%; X = Cl, Br or I.

2. The amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 1, characterized in that, In the aforementioned bifunctional material, the amino group accounts for 10-20% of the material's mass, the quaternary ammonium cation accounts for 5%-15% of the material's mass, and the halide anion accounts for 10-30% of the material's mass; X = I.

3. The amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 1, characterized in that, The bifunctional material structure is a hypercrosslinked multi-level porous polymer with a transverse pore diameter of 1~10 μm and a longitudinal pore width of 5~10 μm and a length of 10~20 μm.

4. The amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 1, characterized in that, The epoxy crosslinking agent is selected from one or more of the following: 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.

5. The amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 1, characterized in that, The molecular weight of the polyethyleneimine mentioned in step (1) is one or more of the following: 600, 1200, 1800, 5000, 10000, 25000, and 70000.

6. The amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 1, characterized in that, The room temperature stirring reaction time in step (1) is 5~50 min; the rapid cooling time in liquid nitrogen is 10~70 min.

7. The amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 1, characterized in that, In step (1), the freezing temperature is -30 ℃ ~ -18 ℃, and the storage time is 1 to 3 days.

8. The application of the amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 1, characterized in that, It is used to directly convert low-concentration carbon dioxide into cyclic carbonates; the volume concentration of low-concentration carbon dioxide is 10%~40%.

9. The application of the amine-ammonium bifunctional material for integrated carbon dioxide capture and utilization as described in claim 8, characterized in that, Includes the following steps: The obtained quaternized supercrosslinked polyethyleneimine material was placed in a reactor, followed by the addition of ethylene oxide and the sealing of the reactor. The gas inlet valve was opened to add 0.1~5 MPa of low-concentration carbon dioxide gas into the reactor. The reaction was stopped after 6~24 h at 25℃~120℃ to obtain the target product ethylene carbonate. For every 1g of quaternized hypercrosslinked polyethyleneimine material, 1~10 mL of ethylene oxide is added.

Images