CN114887594A - Hydrophobic HKUST-1 composite material, preparation method and carbon neutralization application - Google Patents
Hydrophobic HKUST-1 composite material, preparation method and carbon neutralization application Download PDFInfo
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- 239000013148 Cu-BTC MOF Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 6
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000003546 flue gas Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 23
- 239000012621 metal-organic framework Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000002737 fuel gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000009694 intrinsic regeneration Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention relates to a hydrophobic HKUST-1 composite material, a preparation method and carbon neutralization application. The preparation method comprises the following steps: preparing HKUST-1 by a solvent thermosynthesis method; HKUST-1 is used as a carrier to load 2-aminoimidazole to prepare the HKUST-1 composite material. The HKUST-1 composite material prepared by the invention has good hydrophobicity, can effectively protect the metal center of the HKUST-1 composite material, avoids the decomposition effect of water vapor in flue gas, and can be exposed for 20 days under high humidity (90% RH)After that, the performance is only reduced by 20 percent, and the device is provided for trapping CO in the flue for a long time 2 The ability of the cell to perform. The invention has low requirement on equipment, convenient regeneration and simple preparation process, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of gas separation, in particular to a preparation method of a high-hydrophobicity acid-corrosion-resistant MOFs-based composite material and carbon neutralization application.
Background
Large amount of CO 2 Release leads to a continuous increase in the concentration of environmental greenhouse gases (GHG), presenting a significant challenge to global climate and sustainable development. Therefore, it is necessary to extract CO from flue gases and fuel gases (e.g., biomethane and shale gas) 2 To suppress greenhouse gas emissions. Various techniques have been developed to accomplish this task, including cryogenic distillation, membrane separation, chemisorption separation, and physisorption separation. In all of these alternatives described above, adsorptive separation is promising for its energy saving properties, which allows operation at ambient conditions at room temperature. Adsorbents with high capacity and selectivity are the core to facilitate efficient adsorptive separation processes. Therefore, in recent decades, there has been a great deal of interest in the rational design and synthesis of new high performance adsorbents. Aqueous amine is currently the most mature carbon capture technology, but is susceptible to oxidation and thermal degradation, and CO 2 The circulation capacity is low. Porous solid adsorbents, such as zeolites, silica and metal organic frameworks, have been promising CO due to their high surface area, lower intrinsic regeneration energy, higher stability and tunable surface chemistry 2 The material is captured.
Metal Organic Frameworks (MOFs) are a class of crystalline solids with ultra-high surface area, developed porosity, tunable pore size, and tunable chemical function. Research into MOFs has attracted considerable interest in carbon capture and separation applications.
Although the MOFs family is on CO 2 Adsorption shows good results, but in the practical application process, pure MOF powder shows humidity instability due to a small amount of water vapor (7-8%) in a flue, and irreversible structural decomposition can occur, so that the practical application of the pure MOF powder is hindered. Two approaches can be explored to address the moisture stability of MOFs: (i) improving the moisture stability of MOFs by modification and (ii) designing suitable processes for MOF applications without affecting the moisture stability.
The prior patent with the retrieval application number of CN 114146688A introduces a water-resistant HKUST-1/MCFs composite material, which has good water resistance and can convert the negative effect of water vapor in flue gas into positive effect. The adsorption material can reduce environmental pollution, does not corrode equipment, is easy to recycle, and can be used for adsorbing CO 2 Has obvious enhancement in the adsorption amount. It has low requirement on equipment, is convenient to regenerate and is suitable for industrial production. However, it requires the preparation of precursors MCFs first, which increases the number of industrial production steps and increases the cost, and it does not describe the use of the composite material after a long period of use in a high humidity environment.
The prior patent with the retrieval application number of CN 111821955A introduces an MOFs/porous polymer composite material, the composite material realizes the coupling effect of macropores, mesopores and micropores structurally, and the dynamic performance of the material is optimized while the high adsorption performance and the stable adsorption thermodynamic performance are maintained. But in the presence of CO 2 The adsorption capacity is not high, and the disadvantage of hydrophobicity is not provided.
Disclosure of Invention
Aiming at the prior artThe invention aims to provide a preparation method of a hydrophobic HKUST-1 composite material which has cheap raw materials and simple and mild reaction, has better hydrophobic performance, only reduces 20 percent of the performance after being exposed for 20 days under high humidity (90 percent RH), and reduces the performance after CO 2 Has better application in the field of trapping.
The purpose of the invention is realized by the following scheme:
the first aspect of the invention provides a preparation method of a hydrophobic HKUST-1 composite material, which comprises the following steps:
s1, adding a catalyst into deionized water, carrying out ultrasonic treatment to obtain a solution A, adding anhydrous copper nitrate into N, N-dimethylformamide, heating and stirring to obtain a solution B, adding trimesic acid powder into anhydrous ethanol, heating and stirring to obtain a solution C;
s2, slowly adding the solution A into the solution B, marking as a solution D, and heating and stirring;
s3, slowly adding the solution C into the solution D, recording as a solution E, transferring the solution C into a closed container, carrying out hydrothermal reaction, washing a product with absolute ethyl alcohol, centrifuging, and carrying out vacuum drying and activation to obtain HKUST-1;
s4, dissolving 2-aminoimidazole in toluene to prepare a solution F, adding the HKUST-1 obtained from S3 into the solution F, uniformly stirring, and transferring to a conical flask for hydrothermal reaction to obtain a solution G;
s5, washing the solution G with absolute methanol, centrifuging, drying in vacuum, and standing to obtain the HKUST-1 composite material.
Preferably, the catalyst in S1 is zinc oxide.
Preferably, the mass ratio of the zinc oxide, the trimesic acid and the anhydrous copper nitrate in S1 is 1:2.5-3: 4-4.5.
Preferably, the concentration of the solution A in the S1 is 0.2-0.3mol/L, the ultrasonic frequency is 80-120hz, the ultrasonic treatment time is 10-30min, the heating temperature is 25-50 ℃, and the heating and stirring time is 10-30 min.
Preferably, the heating temperature in the S2 is 25-50 ℃, and the heating and stirring time is 10-30 min.
Preferably, the hydrothermal reaction temperature in S3 is 25-50 ℃, the reaction time is 12-24h, the centrifugal rotation speed is 8000-10000rpm, the centrifugal time is 10-30min, the drying temperature is 120-150 ℃, and the drying time is 12-24 h.
Preferably, the concentration of the solution F in the S4 is 0.5-0.6mol/L, the mass ratio of HKUST-1 to 2-aminoimidazole is 1:0.3-0.33, the hydrothermal reaction temperature is 40-60 ℃, and the reaction time is 3-6 h. Too high or too low a reaction temperature leads to CO 2 The adsorption effect is reduced.
Preferably, the centrifugation rotation speed in S5 is 8000-10000rpm, the centrifugation time is 10-30min, the drying temperature is 120-150 ℃, and the drying time is 12-24 h.
The second aspect of the invention provides a hydrophobic HKUST-1 composite material, which is prepared by the preparation method of the hydrophobic HKUST-1 composite material.
In a third aspect, the invention provides an application of a hydrophobic HKUST-1 composite material in carbon neutralization.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the hydrophobic MOFs composite material is simple, mild in reaction condition and environment-friendly, and has the potential of industrial large-scale production.
(2) According to the hydrophobic MOFs composite material, nitrogen atoms on imidazole rings in 2-aminoimidazole can be combined with MOFs unsaturated metal centers to generate intermolecular force, so that hydrolysis and framework collapse caused by combination of the unsaturated metal centers and water molecules are avoided, the performance of the hydrophobic MOFs composite material is only reduced by 20% after the hydrophobic MOFs composite material is exposed for 20 days under high humidity (90% RH), and the hydrophobic MOFs composite material has the function of trapping CO in a flue for a long time 2 The ability of the cell to perform.
(3) The hydrophobic MOFs composite material improves the hydrophobicity, and simultaneously, the amino group carried on the modified material can react with CO 2 Reaction (R-NH) 2 +CO 2 R-NH-CO-OHR), CO thereof 2 The adsorption performance is improved compared with that of pure MOFs.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows the CO concentration in a 90% RH humidity environment according to the present invention 2 Graph of change in adsorption capacity.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1:
dissolving 1g of zinc oxide in 30mL of deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 100hz to obtain a solution A; dissolving 4g of anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 ℃ for 10min to obtain a solution B; dissolving 3g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as a solution C; solution a was slowly added to solution B, the temperature was maintained, stirring was continued, denoted as solution D, and then solution C and solution D were transferred to a ground erlenmeyer flask and stirred vigorously at 25 ℃ for 12 h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at the rotating speed of 8000rpm, and drying and activating for 12h at the temperature of 120 ℃ in vacuum for later use.
Dissolving 0.3g of 2-aminoimidazole in 30mL of toluene, and marking as a solution E; adding activated 1g of HKUST-1 into the solution E, and stirring in a water bath at 40 ℃ for 4 hours; then washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120 deg.C for 12h to obtain hydrophobic 2-aminoimidazole/HKUST-1 composite-1, which contains CO 2 The adsorption effect is shown in table 1.
Example 2:
dissolving 1g of zinc oxide in 30mL of deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 100hz to obtain a solution A; dissolving 4g of anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 ℃ for 10min to obtain a solution B; dissolving 3g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as a solution C; solution a was slowly added to solution B, the temperature was maintained, stirring was continued, denoted as solution D, and then solution C and solution D were transferred to a ground erlenmeyer flask and stirred vigorously at 30 ℃ for 12 h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at the rotating speed of 8000rpm, and drying and activating for 12h at the temperature of 120 ℃ in vacuum for later use.
Dissolving 0.3g of 2-aminoimidazole in 30mL of toluene, and marking as a solution E; adding activated 1g of HKUST-1 into the solution E, and stirring in a water bath at 50 ℃ for 4 hours; then washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120 deg.C for 12h to obtain hydrophobic 2-aminoimidazole/HKUST-1 composite-2, which contains CO 2 The adsorption effect is shown in table 1.
Example 3:
dissolving 1g of zinc oxide in 30mL of deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 100hz to obtain a solution A; dissolving 4g of anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 ℃ for 10min to obtain a solution B; dissolving 3g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as a solution C; solution a was slowly added to solution B, the temperature was maintained, stirring was continued, denoted as solution D, and then solution C and solution D were transferred to a ground erlenmeyer flask and stirred vigorously at 25 ℃ for 12 h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at the rotating speed of 8000rpm, and drying and activating for 12h at the temperature of 150 ℃ in vacuum for later use.
Dissolving 0.3g of 2-aminoimidazole in 30mL of toluene to obtain a solution E; adding activated 1g of HKUST-1 into the solution E, and stirring in a water bath at 60 ℃ for 4 h; then washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 150 deg.C for 12h to obtain hydrophobic 2-aminoimidazole/HKUST-1 composite-3 with CO 2 The adsorption effect is shown in table 1.
Example 4:
dissolving 1g of zinc oxide in 30mL of deionized water, and performing ultrasonic oscillation for 10min at the frequency of 100hz to obtain a solution A; dissolving 4.5g anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 deg.C for 10min to obtain solution B; dissolving 3.5g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as solution C; solution a was slowly added to solution B, the temperature was maintained, stirring was continued, denoted as solution D, and then solution C and solution D were transferred to a ground erlenmeyer flask and stirred vigorously at 25 ℃ for 12 h. After the reaction is finished, obtaining HKUST-1, washing the product with absolute ethyl alcohol for 3 times, centrifuging at 8000rpm for 10min, and drying and activating at 150 ℃ in vacuum for 12h for later use.
Dissolving 0.33g of 2-aminoimidazole in 30mL of toluene, and marking as a solution E; adding activated 1g of HKUST-1 into the solution E, and stirring in a water bath at 60 ℃ for 4 h; then washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 150 deg.C for 12h to obtain hydrophobic 2-aminoimidazole/HKUST-1 composite-4, which has CO content 2 The adsorption effect is shown in table 1.
Comparative example 1:
dissolving 1g of zinc oxide in 30mL of deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 100hz to obtain a solution A; dissolving 4g of anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 ℃ for 10min to obtain a solution B; dissolving 3g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as a solution C; solution a was slowly added to solution B, the temperature was maintained, stirring was continued, denoted as solution D, and then solution C and solution D were transferred to a ground erlenmeyer flask and stirred vigorously at 25 ℃ for 12 h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging at 8000rpm for 10min, drying and activating at 120 ℃ in vacuum for 12h to obtain HKUST-1, CO of which 2 The adsorption effect is shown in table 1.
Comparative example 2:
dissolving 4g of anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 ℃ for 10min to obtain a solution A; dissolving 3g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as a solution B; solution A was slowly added to solution B, the temperature was maintained, stirring was continued, and solution C was then transferred to a ground erlenmeyer flask and stirred vigorously at 25 ℃ for 12 h. After the reaction is finished, obtaining HKUST-1, washing the product with absolute ethyl alcohol for 3 times, centrifuging at 8000rpm for 10min, and drying and activating at 120 ℃ in vacuum for 12h for later use.
Dissolving 0.3g of 2-aminoimidazole in 30mL of toluene, and marking as a solution D; adding activated 1g of HKUST-1 into the solution D, and stirring in a water bath at 40 ℃ for 4 hours; then washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120 deg.C for 12h to obtain hydrophobic 2-aminoimidazole/HKUST-1 composite-5, which contains CO 2 The adsorption effect is shown in table 1.
Comparative example 3:
dissolving 1g of zinc oxide in 30mL of deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 100hz to obtain a solution A; dissolving 4g of anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 ℃ for 10min to obtain a solution B; dissolving 3g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as a solution C; solution a was slowly added to solution B, the temperature was maintained, stirring was continued, denoted as solution D, and then solution C and solution D were transferred to a ground erlenmeyer flask and stirred vigorously at 25 ℃ for 12 h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at the rotating speed of 8000rpm, and drying and activating for 12h at the temperature of 120 ℃ in vacuum for later use.
Dissolving 0.3g of 2-aminoimidazole in 30mL of toluene, and marking as a solution E; adding activated 1g of HKUST-1 into the solution E, and stirring in a water bath at 20 ℃ for 4 h; then washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120 deg.C for 12h to obtain hydrophobic 2-aminoimidazole/HKUST-1 composite-1, which contains CO 2 The adsorption effect is shown in table 1.
Comparative example 4:
dissolving 1g of zinc oxide in 30mL of deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 100hz to obtain a solution A; dissolving 4g of anhydrous copper nitrate in N, N-dimethylformamide, and stirring at 25 ℃ for 10min to obtain a solution B; dissolving 3g of trimesic acid in 30mL of absolute ethanol, stirring for 10min at 25 ℃, and marking as a solution C; solution a was slowly added to solution B, the temperature was maintained, stirring was continued, denoted as solution D, and then solution C and solution D were transferred to a ground erlenmeyer flask and stirred vigorously at 25 ℃ for 12 h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at the rotating speed of 8000rpm, drying and activating for 12h at the temperature of 120 ℃ in vacuum for later use.
Dissolving 0.3g of 2-aminoimidazole in 30mL of toluene, and marking as a solution E; adding activated 1g of HKUST-1 into the solution E, and stirring in a water bath at 80 ℃ for 4 hours; then washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120 deg.C for 12h to obtain hydrophobic 2-aminoimidazole/HKUST-1 composite-1, which contains CO 2 The adsorption effect is shown in table 1.
TABLE 1 product CO 2 Adsorption capacity and high humidity (90% RH) to its CO 2 Adsorption capacityInfluence of the quantity
FIG. 1 shows the CO content of the composite materials of the examples and the comparative examples in a humidity environment of 90% RH 2 Graph of change in adsorption capacity. Comparative example 1 no 2-aminoimidazole was added, and it can be seen from table 1 that the amount of carbon dioxide adsorbed in a high-humidity environment is drastically reduced; in the comparative example 2, the adsorption amount of carbon dioxide is obviously reduced without adding the catalyst zinc oxide; in the comparative example 3, the temperature is lower than 40 ℃, the solubility of the 2-aminoimidazole is lower, the reaction degree is reduced, and the adsorption quantity is reduced to some extent; in comparative example 4, the temperature is higher than 60 ℃, 2-aminoimidazole is partially volatilized, the reaction degree is reduced, and the adsorption quantity is reduced.
In conclusion, the HKUST-1 composite material prepared by the invention has good hydrophobicity, can effectively protect the metal center of the material, avoids the decomposition effect of water vapor in flue gas on the material, can only reduce the performance by 20 percent after being exposed for 20 days under high humidity (90 percent RH), and can capture CO in a flue for a long time 2 The ability of the cell to perform. The invention has low requirement on equipment, convenient regeneration and simple preparation process, and is suitable for industrial production.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. The preparation method of the hydrophobic HKUST-1 composite material is characterized by comprising the following steps of:
s1, adding a catalyst into deionized water, carrying out ultrasonic treatment to obtain a solution A, adding anhydrous copper nitrate into N, N-dimethylformamide, heating and stirring to obtain a solution B, adding trimesic acid powder into anhydrous ethanol, heating and stirring to obtain a solution C;
s2, adding the solution A into the solution B, marking as a solution D, and heating and stirring;
s3, slowly adding the solution C into the solution D, recording as a solution E, transferring the solution C into a closed container, carrying out hydrothermal reaction, washing a product with absolute ethyl alcohol, centrifuging, and carrying out vacuum drying to obtain HKUST-1;
s4, dissolving 2-aminoimidazole in toluene to prepare a solution F, adding the HKUST-1 obtained in the step S3 into the solution F, uniformly stirring, and transferring to a conical flask for hydrothermal reaction to obtain a solution G;
s5, washing the solution G with absolute methanol, centrifuging, and drying in vacuum to obtain the HKUST-1 composite material.
2. The method for preparing hydrophobic HKUST-1 composite material according to claim 1, wherein the catalyst in S1 is zinc oxide.
3. The preparation method of the hydrophobic HKUST-1 composite material according to claim 2, wherein the mass ratio of the zinc oxide, the trimesic acid and the anhydrous copper nitrate is 1:2.5-3: 4-4.5.
4. The preparation method of the hydrophobic HKUST-1 composite material according to claim 1, wherein the concentration of the solution A in the S1 is 0.2-0.3mol/L, the ultrasonic frequency is 80-120hz, the ultrasonic treatment time is 10-30min, the heating temperature is 25-50 ℃, and the heating and stirring time is 10-30 min.
5. The method for preparing the hydrophobic HKUST-1 composite material according to claim 1, wherein the heating temperature in S2 is 25-50 ℃ and the heating and stirring time is 10-30 min.
6. The method for preparing the hydrophobic HKUST-1 composite material as claimed in claim 1, wherein the hydrothermal reaction temperature in S3 is 25-50 ℃, the reaction time is 12-24h, the centrifugation speed is 8000-10000rpm, the centrifugation time is 10-30min, the drying temperature is 120-150 ℃, and the drying time is 12-24 h.
7. The preparation method of the hydrophobic HKUST-1 composite material according to claim 1, wherein the concentration of the solution F in the S4 is 0.5-0.6mol/L, the mass ratio of HKUST-1 to 2-aminoimidazole is 1:0.3-0.33, the hydrothermal reaction temperature is 40-60 ℃, and the reaction time is 3-6 h.
8. The preparation method of the hydrophobic HKUST-1 composite material as claimed in claim 1, wherein the centrifugation speed in S5 is 8000-10000rpm, the centrifugation time is 10-30min, the drying temperature is 120-150 ℃, and the drying time is 12-24 h.
9. A hydrophobic HKUST-1 composite characterized by being produced by the method for producing a hydrophobic HKUST-1 composite as recited in any one of claims 1 to 8.
10. Use of the hydrophobic HKUST-1 composite according to claim 9 for carbon neutralization.
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