CN116212820A - Mixed amine functionalized mesoporous silica solid adsorbent and preparation and application thereof - Google Patents
Mixed amine functionalized mesoporous silica solid adsorbent and preparation and application thereof Download PDFInfo
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- CN116212820A CN116212820A CN202211587627.2A CN202211587627A CN116212820A CN 116212820 A CN116212820 A CN 116212820A CN 202211587627 A CN202211587627 A CN 202211587627A CN 116212820 A CN116212820 A CN 116212820A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003463 adsorbent Substances 0.000 title claims abstract description 75
- 150000001412 amines Chemical class 0.000 title claims abstract description 73
- 239000007787 solid Substances 0.000 title claims abstract description 63
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 42
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 24
- 230000008929 regeneration Effects 0.000 abstract description 11
- 238000011069 regeneration method Methods 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 11
- 238000003795 desorption Methods 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003570 air Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 229940043237 diethanolamine Drugs 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention relates to a mixed amine functionalized mesoporous silica solid adsorbent, and preparation and application thereof, wherein the preparation method comprises the following steps: mixing polyethylenimine and diethanolamine in an organic solvent, adding SBA-15, dipping and stirring at room temperature, and drying to obtain the mixed amine functionalized mesoporous silica solid adsorbent. Compared with the prior art, the mixed amine functionalized solid adsorbent prepared by the invention can be used for directly capturing carbon dioxide from air or indoor environment, and has the characteristics of high adsorption quantity, high adsorption rate, high amine efficiency, low regeneration temperature, good stability, simple preparation process, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of environmental protection and material chemistry, and relates to a method for preparing CO 2 An adsorbed mixed amine functionalized mesoporous silica solid adsorbent, and a preparation method and application thereof.
Background
Human activity has led to global CO for over half a century in the past 2 The emission is increased year by year, the global greenhouse effect is aggravated, and the serious negative effects are brought to the sustainable development of the human living environment and the economic society. CO 2 Environmental climate problems caused by emissions have also prompted governments to bring out a series of policies, techniques and related regulations for carbon emission reduction, and the inter-national government climate change specialization committee (Intergovernmental Panel on Climate Change, IPCC) 2018 issued "IPCC global warming 1.5 ℃ specialization report" has clarified the avoidance of CO 2 The difficulty of exceeding the concentration underscores the importance of the carbon negative emission technique (Negative Emission Technology, NET).
The air carbon trapping technology (Direct air capture, DAC) is used as a representative carbon negative emission technology, so that the defects of high equipment corrosion rate, high regeneration energy consumption, huge absorber volume and the like of the traditional carbon trapping and sealing technology (Carbon capture and storage, CCS) are avoided, and the defects of no storage place and no CO are overcome 2 Transportation restrictions, the device can be placed in places where it has less impact on the environment. Because of its unique advantages, DAC has great application potential in assisting carbon emission reduction. Currently CCS uses primarily Ethanolamine (MEA) solutions and solid porous adsorbents for CO 2 And (5) collecting. The MEA has the problems of high regeneration temperature, large solvent loss, amine volatilization and the like.
Disclosure of Invention
The invention aims to provide a method for CO 2 The mixed amine functionalized mesoporous silica solid adsorbent has the high-efficiency adsorption and low-temperature desorption effects of carbon dioxide, and the desorption regeneration temperature can be reduced to 80 ℃.
The aim of the invention can be achieved by the following technical scheme:
currently, CCS is mainlyCO using ethanolamine (MEA) solution and solid porous adsorbent 2 And (5) capturing. Wherein MEA has the defects of high regeneration temperature, large solvent loss, amine volatilization and the like. While physical adsorption with solid porous adsorbent results in very low CO 2 The capture capacity in ambient air at concentration is low. The mesoporous material SBA-15 can provide a porous carrier for the organic mixed amine, so that the defects of the two modes are avoided, and a feasible scheme is provided for the solid adsorbent with high adsorption rate, high amine efficiency, low regeneration temperature and good stability.
The preparation method of the mixed amine functionalized mesoporous silica solid adsorbent comprises the following steps:
1) Mixing Polyethylenimine (PEI) and Diethanolamine (DEA) in an organic solvent to obtain a mixed amine solution;
2) Adding SBA-15 into the mixed amine solution, dipping and stirring at room temperature, and drying to obtain the mixed amine functional mesoporous silica solid adsorbent.
Further, the mass ratio of the polyethylenimine to the diethanolamine is (0.25-4): 1.
Further, the ratio of the total mass of the polyethylenimine and the diethanol amine to the mass of the SBA-15 is 1 (0.8-1.2).
Further, in the dipping and stirring process, the time is 6-8 hours.
Further, the organic solvent is methanol.
Further, the dosage of the methanol is 18-22mL/g of total mass of the polyethylenimine and the diethanolamine.
Further, the preparation method of the SBA-15 comprises the following steps:
s1: adding Pluronic P123 into hydrochloric acid solution, and uniformly mixing to obtain a surface active template agent solution;
s2: uniformly mixing the surface active template agent solution with tetraethyl silicate, heating and stirring, standing at a high temperature, finally taking a precipitate, and calcining to obtain the SBA-15.
Further, in the step S1, the hydrochloric acid solution is formed by mixing water and 12.1M hydrochloric acid, wherein the mass ratio of Pluronic P123 to water is 1 (25-30), and the using amount of the hydrochloric acid is (3-6) mL/mg Pluronic P123;
in the step S2, in the heating and stirring process, the stirring temperature is 35-45 ℃ and the stirring time is 18-24 hours; the high-temperature standing crystallization temperature is 100-110 ℃, the time is 22-26h, the calcination temperature is 500-600 ℃, and the calcination time is 10-14h.
The mixed amine functionalized mesoporous silica solid adsorbent is prepared by adopting the method.
The application of the mixed amine functionalized mesoporous silica solid adsorbent comprises the step of using the mixed amine functionalized mesoporous silica solid adsorbent for adsorbing CO 2 。
Firstly, mixing polyethylenimine and diethanolamine according to a certain proportion to obtain mixed amine, and then loading the amine on the surface and in pore channels of an SBA-15 carrier by adopting an impregnation method. The mixed amine functionalized solid adsorbent can be used to capture carbon dioxide directly from air or indoor environments. The mixed amine functionalized solid adsorbent prepared by the method has the characteristics of high adsorption quantity, high adsorption rate, high amine efficiency, low regeneration temperature, good stability, simple manufacturing process, low cost and the like.
Compared with the prior art, the invention has the following characteristics:
1) The organic amine modified composite material of the invention uses SBA-15 to CO 2 The mechanism of (2) is changed from pure physical adsorption to chemical physical adsorption, thereby improving the CO content of the adsorbent 2 Adsorption performance under extremely dilute concentration conditions;
2) Due to the synergistic effect of PEI and DEA in the solid adsorbent, the PEI improves the thermal stability of the DEA in the mixed amine component, and the DEA optimizes the distribution of PEI on the carrier SBA-15;
3) Due to the synergistic effect of hydroxyl groups in the solid adsorbent and the mixed amine, the mixed amine solid adsorbent has higher amine efficiency than the solid adsorbent simply loaded with PEI or DEA, which also means that the mixed amine solid adsorbent has stronger CO 2 Adsorption performance;
4) The desorption regeneration temperature is reduced to 80 ℃, so that the energy consumption is further reduced, and the possibility of further reduction exists, thereby being beneficial to the economic feasibility of the DAC;
5) The manufacturing method is simple, has low cost, can be used for large-scale production, and is easy for industrial realization.
Drawings
FIG. 1 is a flow chart of a novel mixed amine functionalized mesoporous silica solid adsorbent according to the present invention;
FIG. 2 is a photograph of a sample of a novel mixed amine functionalized mesoporous silica solid adsorbent of example 1 under a Scanning Electron Microscope (SEM);
FIG. 3 is a Fourier transform infrared absorption spectrum (FTIR) test results of a solid adsorbent sample of example 1 having a weight ratio of PEI to DEA of 1:1 at 50wt.% polyamine loading;
FIG. 4 is the SEM analysis results of a solid adsorbent sample loaded with PEI alone at a weight ratio of PEI to DEA of 1:1 under an amine loading of 50 wt.%;
FIG. 5 is a graph of simulated air (400 ppm CO) at 25 ℃ 2 /N 2 ) Under the condition that PEI and DEA are sample test results of the adsorption capacity (quasi-static adsorption capacity) of the mixed amine functionalized mesoporous silica solid adsorbent at different mass ratios;
FIG. 6 is a graph of simulated air (400 ppm CO) at 25 ℃ 2 /N 2 ) Under the condition that PEI and DEA are sample test results of adsorption power (adsorption rate) of the mixed amine functionalized mesoporous silica solid adsorbent at different mass ratios;
FIG. 7 is a graph of CO at 25℃for an S/P1 adsorbent 2 Adsorption and desorption curves at different degassing temperatures;
FIG. 8 is a graph of CO at 25℃for the S/P1/D1 adsorbent 2 Adsorption and desorption curves at different degassing temperatures.
The figure indicates:
1-Pluronic P123; 2-hydrochloric acid solution; 3-a surface active templating agent solution; 4-tetraethyl silicate; 5-precipitate; 6-SBA-15;7-PEI;8-DEA; 9-methanol; 10-PEI/DEA mixed amine solution; 11-PEI/DEA mixed polyamine functionalized SBA-15 adsorbent.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The preparation method of the mixed amine functionalized mesoporous silica solid adsorbent shown in fig. 1 comprises the following steps:
1) Preparation of SBA-15:
1-1) adding Pluronic P123 1 into a hydrochloric acid solution 2 formed by mixing water and 12.1M hydrochloric acid, and uniformly mixing to obtain a surface active template agent solution 3; wherein the mass ratio of Pluronic P123 to water is 1 (25-30), and the dosage of hydrochloric acid is (3-6) mL/mg Pluronic P123;
1-2) uniformly mixing the surface active template agent solution 3 and the tetraethyl silicate 4, heating and stirring for 20-28h at 35-45 ℃, standing for 22-26h at 100-110 ℃, finally taking a precipitate 5, and calcining for 10-14h at 500-600 ℃ to obtain SBA-15;
2) Preparation of mixed amine functionalized solid adsorbent:
mixing PEI 7 and DEA 8 in a mass ratio of (0.25-4): 1 (preferably a mass ratio of 1:1) in an organic solvent methanol 9 to obtain a mixed amine solution 10; adding SBA-15 6, dipping and stirring for 6-8 hours at room temperature, and drying to obtain the PEI/DEA mixed polyamine functionalized SBA-15 adsorbent 11;
wherein the dosage of the methanol is 18-22mL/g of mixed amine (preferably 20mL/g of mixed amine), the mass ratio of the mixed amine to SBA-15 is 1 (0.8-1.2), and the preferred mass ratio is 1:1.
The application of the mixed amine functionalized mesoporous silica solid adsorbent comprises the step of using the mixed amine functionalized mesoporous silica solid adsorbent for adsorbing CO 2 In particular CO in air or in a room 2 A gas; the adsorption temperature is 25 ℃, the optimal desorption regeneration temperature is 80 ℃, and the possibility of further reduction is provided.
The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the solid adsorbents of the following examples, the synthesized mixed amine-functionalized mesoporous silica solid adsorbent was designated as S/Px/Dy, where S represents SBA-15 and x/y represents the weight ratio of PEI (P) to DEA (D).
Example 1:
the preparation method of the mixed amine functionalized mesoporous silica solid adsorbent S/P1/D1 comprises the following steps:
1) 24g Pluronic P123 (average molecular weight 5800) surfactant was dissolved in a solution of 636g deionized water and 120mL 12.1M HCl and vigorously stirred at 1000rpm for 3h at 25 ℃;
the resulting solution was heated to 40 ℃, 46.6g of tetraethyl silicate (Tetraethyl orthosilicate, TEOS, 99% purity, average molecular weight 208.33) was added dropwise, stirred at 1000rpm for 20h, then heated to 100 ℃ and held for 24h, the resulting precipitate was filtered, washed with 400mL of deionized water, and dried at 75 ℃ for 12h;
finally, calcining at 550 ℃ for 12 hours to obtain SBA-15;
2) Dissolving PEI with the total mass of 0.25g and DEA with the total mass of 0.25g in 10mL of methanol, and stirring at 800rpm for 1h to obtain a mixed amine solution; adding 0.5g of dry SBA-15 to the mixed amine solution and stirring at room temperature for 6 hours;
thereafter, the suspension was subjected to rotary evaporation operation, the remaining solid powder was collected and dried in vacuum (< 20 mTorr) at 25℃for 12 hours to obtain PEI/DEA mixed polyamine functionalized SBA-15 adsorbent S/P1/D1.
FIG. 2 is a photograph of a sample of the novel mixed amine functionalized mesoporous silica solid adsorbent of example 1 under a scanning electron microscope.
The FTIR test was performed on S/P1/D1 and the results are shown in fig. 3 as sample test results for solid adsorbents with a weight ratio of PEI to DEA of 1:1 at 50wt.% polyamine loading. At 1079cm -1 ，802cm -1 And 459cm -1 Absorbance peaks were observed at 1637cm, which were caused by the vibration of the skeleton of the mesoporous silica main structure -1 And 1476cm -1 Infrared bands are observed at the positions corresponding to-NH respectively 2 and-NH, demonstrated that the solid adsorbent was successfully loaded with the mixed amine and that the structure of the mesoporous silica was unchanged.
Example 2:
the preparation method of the mixed amine functionalized mesoporous silica solid adsorbent is different from that of the embodiment 1 only in that:
and respectively taking 0.5g PEI, 0.25g PEI and 0.25g DEA as modified amine to respectively prepare a single amine functional mesoporous silica solid adsorbent S/P1 and a mixed amine functional mesoporous silica solid adsorbent S/P1/D1.
SEM analysis was performed on S/P1 and S/P1/D1, respectively, and the analysis results are shown in FIG. 4-a and FIG. 4-b, respectively, where FIG. 4-a is a sample test result of the adsorbent S/P1 and FIG. 4-b is a sample test result of the solid adsorbent S/P1/D1 under a polyamine load of 50 wt.%. It was observed that PEI covered the outer surface of SBA-15 or filled in between the pores, resulting in agglomeration of the adsorbent, while the introduction of DEA could alleviate agglomeration of the polyamine on the support, optimizing its distribution, resulting in an adsorbent with better microstructural properties.
Example 3: influence of the weight ratio of PEI to DEA on the adsorption Properties
The preparation method of the mixed amine functionalized mesoporous silica solid adsorbent is different from that of the embodiment 1 only in that:
maintaining polyamine loading at 50wt%, namely about 0.5g total amount of DEA and PEI, adjusting PEI dosage to make weight ratio of PEI (P) to DEA (D) be 1:4,1:2,1:1,2:1,4:1, respectively, and preparing adsorbent S/P1/D4, S/P1/D2, S/P1/D1, S/P2/D1 and S/P4/D1;
the amount of DEA is 0.5g, and PEI is not added to prepare the adsorbent S/D1;
PEI is used in an amount of 0.5g, and DEA is not added to prepare an adsorbent S/P1;
the procedure is as in example 1.
Using a thermogravimetric analyzer (TGA), the air (400 ppm CO) was simulated 2 The balance being N 2 ) The adsorption capacity test of the mixed amine functionalized mesoporous silica solid adsorbent was performed in an atmosphere at 25 ℃ and the results are shown in fig. 5, and are the results of sample test of the solid adsorbent at different mass ratios of PEI to DEA under an amine load of 50 wt.%. It can be observed that at 50wt.% polyamine loading, the weight of PEI and DEAThe solid adsorbent having a ratio of 4:1 showed the largest CO at an adsorption time of 2 hours 2 Adsorption capacity 1.62mmol/g and maximum amine efficiency 0.199mmol CO 2 /mmol N。
This example also includes the adsorption kinetics test of the solid adsorbents described above, and the results are shown in FIG. 6. FIG. 6 is a sample test of the solid adsorbents at 50wt.% amine loading with PEI and DEA at different mass ratios. It can be observed that the introduction of DEI significantly increases the duration of the initial rate peak and that it is longest at a weight ratio of PEI to DEA of 1:1, which also means that S/P1/D1 will have the best cyclic reaction performance.
Example 4: evaluation of Desorption Performance
The desorption performance was evaluated for S/P1 and S/P1/D1 saturated with carbon dioxide adsorption in example 2, as shown in FIGS. 7 and 8, and the specific results are shown in Table 1 below.
TABLE 1
| Adsorbent designation | S/P1 | S/P1/D1 |
| Optimum regeneration temperature (. Degree. C.) | 90 | 80 |
As can be seen from Table 1, the mixed amine functionalized mesoporous silica solid adsorbent provided by the invention is used for adsorbing CO 2 At this time, the desorption regeneration temperature may be reduced to 80 ℃.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the mixed amine functionalized mesoporous silica solid adsorbent is characterized by comprising the following steps of:
1) Mixing polyethyleneimine and diethanolamine in an organic solvent to obtain a mixed amine solution;
2) Adding SBA-15 into the mixed amine solution, dipping and stirring at room temperature, and drying to obtain the mixed amine functional mesoporous silica solid adsorbent.
2. The method for preparing the mixed amine functionalized mesoporous silica solid adsorbent according to claim 1, wherein the mass ratio of the polyethylenimine to the diethanolamine is (0.25-4): 1.
3. The preparation method of the mixed amine functionalized mesoporous silica solid adsorbent according to claim 1, wherein the ratio of the total mass of polyethylenimine and diethanolamine to the mass of SBA-15 is 1 (0.8-1.2).
4. The method for preparing the mixed amine functionalized mesoporous silica solid adsorbent according to claim 1, wherein the time is 6-8h in the dipping and stirring process.
5. The method for preparing a mixed amine functionalized mesoporous silica solid adsorbent according to claim 1, wherein the organic solvent is methanol.
6. The method for preparing the mixed amine functionalized mesoporous silica solid adsorbent according to claim 5, wherein the dosage of the methanol is 18-22mL/g of the total mass of the polyethylenimine and the diethanolamine.
7. The method for preparing the mixed amine functionalized mesoporous silica solid adsorbent according to claim 1, wherein the method for preparing the SBA-15 comprises the following steps:
s1: adding Pluronic P123 into hydrochloric acid solution, and uniformly mixing to obtain template agent solution;
s2: and uniformly mixing the template agent solution with tetraethyl silicate to obtain gel, heating and stirring, standing at a high temperature, and finally taking and calcining a precipitate to obtain the SBA-15.
8. The method for preparing the mixed amine functionalized mesoporous silica solid adsorbent according to claim 7, wherein in the step S1, the hydrochloric acid solution is formed by mixing water and 12.1M hydrochloric acid, wherein the mass ratio of Pluronic P123 to water is 1 (25-30), and the use amount of hydrochloric acid is (3-6) mL/mg Pluronic P123;
in the step S2, in the heating and stirring process, the stirring temperature is 35-45 ℃ and the stirring time is 18-24 hours; the high-temperature standing crystallization temperature is 100-110 ℃, the time is 22-26h, the calcination temperature is 500-600 ℃, and the calcination time is 10-14h.
9. A mixed amine functionalized mesoporous silica solid adsorbent prepared by the method of any one of claims 1 to 8.
10. The use of a mixed amine functionalized mesoporous silica solid adsorbent according to claim 9, wherein the mixed amine functionalized mesoporous silica solid adsorbent is used for adsorbing CO 2 。
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| 何志军 等: "《混合胺功能化SBA-15空气碳捕集吸附剂性能研究》", 《第一届全国碳中和与绿色发展大会》, 12 November 2021 (2021-11-12), pages 2 - 1 * |
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