CN111644155A - Efficient adsorption of CO2Preparation method and application of two-dimensional MOFs material - Google Patents
Efficient adsorption of CO2Preparation method and application of two-dimensional MOFs material Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 239000003546 flue gas Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- -1 1-ethylamino-3-methylimidazole bromide salt Chemical compound 0.000 claims description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- PKWKZPOEJCQSHI-UHFFFAOYSA-N CCNN1C=CN(C)C1.Cl Chemical compound CCNN1C=CN(C)C1.Cl PKWKZPOEJCQSHI-UHFFFAOYSA-N 0.000 claims description 4
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- GXXRRENCFHCXNL-UHFFFAOYSA-N CCCNN1C=CN(C)C1.Cl Chemical compound CCCNN1C=CN(C)C1.Cl GXXRRENCFHCXNL-UHFFFAOYSA-N 0.000 claims description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013336 microporous metal-organic framework Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- MSMZCSQFUQHXMN-UHFFFAOYSA-M N-ethyl-3-methylimidazol-3-ium-1-amine chloride Chemical compound [Cl-].C(C)N[N+]1=CN(C=C1)C MSMZCSQFUQHXMN-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- VEYRUOSTCSDWLK-UHFFFAOYSA-N 1-(1-methylimidazol-2-yl)propane-1-sulfonic acid Chemical compound S(=O)(=O)(O)C(CC)C1=NC=CN1C VEYRUOSTCSDWLK-UHFFFAOYSA-N 0.000 description 2
- ONRREFWJTRBDRA-UHFFFAOYSA-N 2-chloroethanamine;hydron;chloride Chemical compound [Cl-].[NH3+]CCCl ONRREFWJTRBDRA-UHFFFAOYSA-N 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- XMBVAOYEIKCBJI-UHFFFAOYSA-M N-ethyl-3-methylimidazol-3-ium-1-amine bromide Chemical compound [Br-].C(C)N[N+]1=CN(C=C1)C XMBVAOYEIKCBJI-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WJAXXWSZNSFVNG-UHFFFAOYSA-N 2-bromoethanamine;hydron;bromide Chemical compound [Br-].[NH3+]CCBr WJAXXWSZNSFVNG-UHFFFAOYSA-N 0.000 description 1
- RMHQDKYZXJVCME-UHFFFAOYSA-N 2-pyridin-4-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=NC=C1 RMHQDKYZXJVCME-UHFFFAOYSA-N 0.000 description 1
- DHXNZYCXMFBMHE-UHFFFAOYSA-N 3-bromopropanoic acid Chemical compound OC(=O)CCBr DHXNZYCXMFBMHE-UHFFFAOYSA-N 0.000 description 1
- IHPRVZKJZGXTBQ-UHFFFAOYSA-N 3-chloropropan-1-amine;hydron;chloride Chemical compound Cl.NCCCCl IHPRVZKJZGXTBQ-UHFFFAOYSA-N 0.000 description 1
- NFPFYKJFRXNJAZ-UHFFFAOYSA-M 3-methyl-N-propylimidazol-3-ium-1-amine chloride Chemical compound [Cl-].C(CC)N[N+]1=CN(C=C1)C NFPFYKJFRXNJAZ-UHFFFAOYSA-M 0.000 description 1
- QBXWHDJGONEWLK-UHFFFAOYSA-N [Br].C(C)NN1CN(C=C1)C Chemical compound [Br].C(C)NN1CN(C=C1)C QBXWHDJGONEWLK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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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- 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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Abstract
The invention discloses a method for efficiently adsorbing CO2The preparation method and the application of the two-dimensional MOFs material. The method is characterized in that water or methanol is used as a medium, metal salt, functionalized ionic liquid and nitrogen heterocyclic organic ligand are mixed, stirred and reacted for 24-48 hours at 25-60 ℃, and spontaneously assembled to form the two-dimensional microporous MOFs material. The material can simulate flue gas (CO) at normal temperature and normal pressure2/N2) Middle and high efficiency CO capture2. The method integrates the functions of ionic liquid and the advantages of large specific surface area, high stability and the like of the two-dimensional MOFs material, and is an adsorption material with great industrial application potential.
Description
Technical Field
The invention relates to a method for efficiently adsorbing CO2Belonging to the technical field of material chemistry and environment.
Background
With the rapid development of global economy, the industrial tail gas produced by the combustion of fossil fuels in industry is CO2Long-term, stable, centralized emission source. However, CO in conventional flue gas of fuel gas, fuel oil and coal2Lower concentration (8-15 vol.%), from N at lower pressure2Separation of CO at lower concentration from gas mixture as main component2The gas has technical bottlenecks of high difficulty, high energy consumption, high cost and the like. Development of CO2High efficiency adsorption/separation material for CO2The important precondition of source enrichment and further resource high-value utilization.
Two-dimensional metal organic framework Materials (MOFs) are a novel porous crystal material which is rapidly developed in recent years, have the advantages of large specific surface area, high porosity, regular pore channels, designable structure and performance and the like, and are applied to CO2The adsorption field exhibits unique advantages. The two-dimensional MOFs material not only has the advantages of the MOFs material, but also has the advantages of high external specific surface area, many active sites and the like, and can further improve the adsorption performance.
Disclosure of Invention
The invention aims to provide a method for efficiently adsorbing CO2The preparation method and the application of the two-dimensional MOFs material.
The invention uses ionic liquid as bifunctional agent, on one hand, as monodentateThe regulating agent is assembled in the MOFs material framework in situ to induce the formation of the two-dimensional MOFs material, and on the other hand, CO is rapidly and reversibly fixed2Effectively improve the material pair CO2Adsorption selectivity and adsorption capacity.
The invention provides a method for efficiently adsorbing CO2The preparation method of the two-dimensional MOFs material is characterized by taking water or methanol as a medium, mixing metal salt, functionalized ionic liquid and nitrogen heterocyclic organic ligand, stirring and reacting at 25-60 ℃ for 24-48 h, centrifuging, washing with deionized water (washing for 3 times and 30mL each time), and vacuum drying at 70 ℃ for 12h to obtain the two-dimensional MOFs material.
In the method, the functionalized ionic liquid is any one of 1-ethylamino-3-methylimidazole chloride salt, 1-ethylamino-3-methylimidazole bromide salt, 1-propylamino-3-methylimidazole chloride salt, 1-sulfopropyl-3-ethylimidazole inner salt and 1-propylcarboxyl-3-methylimidazole bromide salt. The synthesis process of each functionalized ionic liquid is as follows:
1-ethylamino-3-methylimidazolium chloride salt: respectively weighing 1.64-4.11 g (20-50 mmol) of N-methylimidazole and 2.3-5.8 g (20-50 mmol) of 2-chloroethylamine hydrochloride, adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 8 hours. Filtering to obtain a solid, washing with absolute ethyl alcohol, and vacuum drying for 12h to obtain 1-ethylamino-3-methylimidazole chloride salt;
1-ethylamino-3-methylimidazolium bromide salt: weighing 1.64-4.11 g (20-50 mmol) of N-methylimidazole and 4.1-10.2 g (20-50 mmol) of 2-bromoethylamine hydrobromide respectively, adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 8 hours. Filtering to obtain a solid, washing with absolute ethyl alcohol, and vacuum drying for 12h to obtain 1-ethylamino-3-methylimidazole bromine salt;
1-propylamino-3-methylimidazolium chloride salt: respectively weighing 1.64-4.11 g (20-50 mmol) of N-methylimidazole and 1.89-4.723 g (20-50 mmol) of 3-chloropropylamine hydrochloride, adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 8 hours. Filtering to obtain a solid, washing with absolute ethyl alcohol, and vacuum drying for 12h to obtain 1-propylamine-3-methylimidazole chloride salt;
1-sulfopropyl-3-methylimidazole inner salt: dissolving 1.64-4.11 g (20-50 mmol) of N-methylimidazole in 10-20 mL of acetonitrile, and then dropwise adding a 20-30 mL toluene solution in which 2.44-6.1 g (20-50 mmol) of 1, 3-propylsultone is dissolved under the ice bath and stirring state. After the completion of the dropwise addition, the temperature was raised to 50 ℃ and the reaction was carried out for 2 hours. After the reaction is finished, naturally cooling to room temperature, filtering, washing the white solid with diethyl ether for 3 times, and finally drying in vacuum at 50 ℃ for 12 hours to obtain 1-sulfopropyl-3-methylimidazole inner salt;
1-propylcarboxy-3-methylimidazolium bromide salt: weighing 1.64-4.11 g (20-50 mmol) of N-methylimidazole and 3.06-7.65 g (20-50 mmol) of 3-bromopropionic acid respectively, adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 12 hours. Filtering to obtain a solid, washing with absolute ethyl alcohol, and vacuum drying for 12h to obtain the 1-propyl carboxyl-3-methylimidazole bromine salt.
The nitrogen heterocyclic organic ligand in the method is any one of imidazole, 2-methylimidazole and 4, 4' -bipyridine.
The metal salt in the method is any one of zinc nitrate hexahydrate, chromium nitrate nonahydrate and copper nitrate hexahydrate.
The preparation method is characterized in that the molar use ratio of the functionalized ionic liquid to the heterocyclic nitrogen organic ligand is 1: 1.5-20; the molar use ratio of the metal salt to the nitrogen heterocyclic organic ligand is 1: 4-8, and the molar ratio of the solvent to the organic ligand is 1-8: 1; the solvent is methanol or water.
The invention provides a method for preparing two-dimensional MOFs material for trapping low-concentration CO in simulated flue gas2The use of (1).
In the application, the simulated flue gas component is CO2And N2，CO2The content is 15vol.%, the inlet gas pressure is regulated to be 1-5 bar, and the inlet gas flow rate is 100-120 mL/min-1The temperature of the adsorption column is 25-75 ℃, and downstream gas components are monitored on line through a gas infrared analyzer.
The invention has the beneficial effects that:
the invention provides a preparation method of an ionic liquid functionalized two-dimensional MOFs material, which has the advantages of simple preparation process, short period, small dosage of the ionic liquid and low preparation cost; what is needed isThe prepared two-dimensional MOFs material has CO2High selectivity, large adsorption capacity, strong cycle stability and the like, and has great application potential.
Drawings
FIG. 1 shows CO2Schematic diagram of adsorption experimental apparatus.
In the figure: 1 is a gas cylinder, 2 is a pressure gauge, 3 is a valve, 4 is a flow controller, 5 is a thermostat, 6 is a temperature controller, 7 is an adsorbent, 8 is CO2An analyzer.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
4.11g of N-methylimidazole and 5.8g of 2-chloroethylamine hydrochloride are respectively weighed, added into 30ml of anhydrous acetonitrile, introduced with nitrogen for protection, and subjected to reflux reaction for 8 hours. Filtering to obtain a solid, washing with absolute ethyl alcohol, and vacuum drying for 12h to obtain the 1-ethylamino-3-methylimidazole chloride salt.
1-ethylamino-3-methylimidazolium chloride salt (0.5mmol, 0.0808g), zinc nitrate hexahydrate (1.25 mmol, 0.375 g) and imidazole (10 mmol, 0.6808 g) were weighed out and dissolved in 25ml of water, followed by reaction with stirring at 50 ℃ for 24 hours. After the reaction was complete, centrifugation, deionized water washing (3X 30 mL), and vacuum drying at 70 ℃ for 12h was performed, and the name MOF-IL-1 was obtained.
Example 2:
in the same manner as in example 1, 1-sulfopropyl-3-ethylimidazole inner salt (0.5mmol, 0.1232 g) was used instead of 1-ethylamino-3-methylimidazolium chloride salt, and the other conditions were unchanged to obtain MOF-IL-2.
Example 3:
in the same manner as in example 1, 1-ethylamino-3-methylimidazolium bromide (0.5mmol, 0.103 g) was used instead of 1-ethylamino-3-methylimidazolium chloride, and the other conditions were not changed to obtain MOF-IL-3.
Example 4:
similar to example 1, the reaction solvent was adjusted to methanol (25 ml) and other conditions were unchanged to give MOF-IL-4.
Example 5:
similar to example 2, the reaction temperature was adjusted to 25 ℃ and other conditions were unchanged to obtain MOF-IL-5.
Example 6:
as in example 2, replacing the zinc nitrate hexahydrate by copper nitrate hexahydrate (1.25 mmol, 0.3345 g) with the other conditions unchanged provided MOF-IL-6.
Example 7:
as in example 2, 4' -bipyridine (10 mmol, 1.5618 g) was substituted for imidazole, and other conditions were unchanged to give MOF-IL-7.
Example 8:
as in example 1, 2-methylimidazole (10 mmol, 0.821 g) was substituted for the imidazole and the conditions were otherwise unchanged to give MOF-IL-8.
Further prepares the MOFs material without doping the ionic liquid as comparison
Comparative example 1
Zinc nitrate hexahydrate (1.25 mmol, 0.375 g) and 2-methylimidazole (10 mmol, 0.821 g) were weighed out and dissolved in 25ml of methanol and reacted at 25 ℃ for 24 hours with stirring. After the reaction was complete, centrifugation, washing with deionized water (3X 30 mL), and vacuum drying at 70 ℃ for 12h was performed, and the name MOF-1 was obtained.
Comparative example 2
As in comparative example 1, replacing the zinc nitrate hexahydrate by copper nitrate hexahydrate (1.25 mmol, 0.3345 g) with the other conditions unchanged gave MOF-2.
Comparative example 3
Similar to comparative example 1, substituting 4, 4' -bipyridine (10 mmol, 1.5618 g) for 2-methylimidazole, with other conditions unchanged, gave MOF-3.
Comparative example 4
As in comparative example 1, imidazole (10 mmol, 0.6808 g) was substituted for 2-methylimidazole, and other conditions were unchanged to give MOF-4.
Comparative example 5
In the same manner as in comparative example 1, the reaction solvent was adjusted to water (25 ml) and other conditions were unchanged to give MOF-5.
Comparative example 6
In the same way as in comparative example 1, the reaction temperature was adjusted to 25 ℃ and other conditions were unchanged to obtain MOF-6.
With N2/CO2The mixed gas simulates flue gas, and researches CO of two-dimensional MOFs material2And (4) adsorption performance.
Application example 1
Two-dimensional MOF material to CO is carried out on a self-built fixed bed adsorption device2Study of adsorption Performance, the apparatus is shown in FIG. 1.
Weighing 0.1g MOF-IL-1, loading into adsorption column, and introducing at flow rate of 100mL min-1N of (A)2And purging at 140 ℃ for 1 h. Filling the sample into an adsorption column, cooling the adsorption column to an adsorption temperature of 25 ℃, and switching the inlet gas to a mixed gas (15 vol.% CO)2) The flow rate is 100 mL/min-1Measuring CO2The adsorption amount of (B) was 2.5 mmol/g-1。
Application example 2
In the same way as in application example 1, the MOF-IL-1 was replaced with MOF-IL-2, and CO was measured under otherwise unchanged conditions2The adsorption amount of (B) was 2.8 mmol/g-1。
Application example 3
In the same way as in application example 1, the MOF-IL-1 was replaced with MOF-IL-3, and CO was measured under otherwise unchanged conditions2The adsorption amount of (B) was 2.7 mmol/g-1。
Application example 4
In the same way as in application example 1, the MOF-IL-1 was replaced with MOF-IL-4, and CO was measured under otherwise unchanged conditions2The adsorption amount of (B) was 3.1 mmol/g-1。
Application example 5
In the same way as in application example 1, the MOF-IL-1 was replaced with MOF-IL-5, and CO was measured under otherwise unchanged conditions2The adsorption amount of (B) was 2.5 mmol/g-1。
Application example 6
In the same way as in application example 1, the MOF-IL-1 was replaced with MOF-IL-6, and CO was measured under otherwise unchanged conditions2The adsorption amount of (B) was 3.0 mmol/g-1。
TABLE 1 CO of MOF-IL-X2Amount of adsorption
Selecting CO2Adsorption propertyThe MOF-IL-4 with excellent performance is further researched, and the influence of temperature on the adsorption performance of the material is further researched.
Application example 7
In the same application example 1, the adsorption temperature was adjusted to 50 ℃ and the CO was measured under the same conditions as those in the previous example2The adsorption amount of (B) was 3.2 mmol/g-1。
Application example 8
In the same application example 1, the adsorption temperature was adjusted to 75 ℃ and the CO was measured under the same conditions as those in the previous example2The adsorption amount of (B) was 3.4mmol/g-1。
Application example 9
In the same application example 1, the adsorption temperature was adjusted to 90 ℃ and the CO was measured under the same conditions as those in the previous example2The adsorption amount of (B) was 2.9 mmol/g-1。
TABLE 2 MOF-IL-4 CO at different temperatures2Amount of adsorption
Selecting CO2MOF-IL-4 with excellent adsorption performance is further researched for CO by two-dimensional MOFs material2Adsorptive cycle performance
Application example 11
Weighing 0.1g MOF-IL-4, loading into adsorption column, and introducing at flow rate of 100 mL/min-1N of (A)2And purging at 140 ℃ for 1 h. Filling the sample into an adsorption column, cooling the adsorption column to an adsorption temperature of 25 ℃, and switching the inlet gas to a mixed gas (15 vol.% CO)2) The flow rate is 100 mL/min-1After equilibrium of adsorption, CO is measured2The amount of adsorption. Continuously heating to 140 ℃, and introducing 100 mL/min of flow-1N of (A)2And purging at 140 ℃ for 1 h. The cycle was 10 times. The recycling results are shown in table 3.
TABLE 3 MOF-IL-4 CO2Cyclic adsorption regime
Further comparing the MOF material CO not doped with ionic liquid2Adsorption Property
Comparative example 1
In the same way as in application example 1, the MOF-IL-1 was replaced with MOF-1, and the CO was measured under otherwise unchanged conditions2The adsorption amount of (B) was 1.7 mmol. multidot.g-1。
Comparative example 2
In the same way as in comparative example 1, instead of MOF-1, MOF-2, other conditions were unchanged and CO was determined2The adsorption amount of (B) was 1.4 mmol/g-1。
Comparative example 3
In the same way as in comparative example 1, replacing MOF-1 with MOF-3, and under the same other conditions, CO was measured2The adsorption amount of (B) was 1.5 mmol/g-1。
Comparative example 4
In the same way as in comparative example 1, replacing MOF-1 with MOF-4, the other conditions were not changed, and CO was measured2The adsorption amount of (B) was 1.5 mmol/g-1。
Comparative example 5
In the same way as in comparative example 1, replacing MOF-1 with MOF-5, the other conditions were not changed, and CO was measured2The adsorption amount of (b) was 1.8 mmol/g-1。
Comparative example 6
In the same way as in comparative example 1, instead of MOF-1, MOF-6, other conditions were unchanged and CO was determined2The adsorption amount of (B) was 1.7 mmol. multidot.g-1。
TABLE 4 CO of MOF-X2Amount of adsorption
Therefore, compared with the MOFs material which is not doped with the ionic liquid, the ionic liquid functionalized two-dimensional MOFs material prepared by the method disclosed by the invention has the advantages that CO is contained in the ionic liquid functionalized two-dimensional MOFs material2The adsorption performance is obviously improved. The adsorption capacity of the material can reach 3.4mmol/g at most, and the high-efficiency adsorption can be kept in both a low-temperature area and a high-temperature area.
Several highly effective CO were prepared in the above examples2Adsorbent realizes the reaction of CO2High selectivity, large capacity, low energy capture of CO2In particular CO in flue gases2The fixed transformation of (a) provides an efficient process.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the detailed description is made with reference to the embodiments of the present invention, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which shall be covered by the claims.
Claims (8)
1. Efficient adsorption of CO2The preparation method of the two-dimensional MOFs material is characterized by comprising the following steps: the metal salt, the functionalized ionic liquid and the nitrogen heterocyclic organic ligand are mixed by taking water or methanol as a medium, stirred and reacted for 24-48 h at 25-60 ℃, centrifuged, washed by deionized water and dried for 12h under vacuum at 70 ℃ to obtain the metal salt.
2. The efficient adsorption of CO of claim 12The preparation method of the two-dimensional MOFs material is characterized by comprising the following steps: the functionalized ionic liquid is any one of 1-ethylamino-3-methylimidazole chloride salt, 1-ethylamino-3-methylimidazole bromide salt, 1-propylamino-3-methylimidazole chloride salt, 1-sulfopropyl-3-ethylimidazole inner salt and 1-propylcarboxyl-3-methylimidazole bromide salt.
3. The efficient adsorption of CO of claim 12The preparation method of the two-dimensional MOFs material is characterized by comprising the following steps: the nitrogen heterocyclic organic ligand is any one of imidazole, 2-methylimidazole and 4, 4' -bipyridine.
4. The efficient adsorption of CO of claim 12The preparation method of the two-dimensional MOFs material is characterized by comprising the following steps: the metal salt is any one of zinc nitrate hexahydrate, chromium nitrate nonahydrate and copper nitrate hexahydrate.
5. The efficient adsorption of CO of claim 12The preparation method of the two-dimensional MOFs material is characterized by comprising the following steps: the mole of the functionalized ionic liquid and the nitrogen heterocyclic organic ligandThe dosage ratio is 1: 1.5-20; the molar use ratio of the metal salt to the nitrogen heterocyclic organic ligand is 1: 4-8.
6. The efficient adsorption of CO of claim 12The preparation method of the two-dimensional MOFs material is characterized by comprising the following steps: the molar ratio of the solvent to the organic ligand is 1-8: 1; the solvent is methanol or water.
7. Two-dimensional MOFs material prepared by the preparation method of any one of claims 1 to 6 and used for capturing low-concentration CO in simulated flue gas2The use of (1).
8. Use according to claim 7, characterized in that: the simulated flue gas component is CO2And N2，CO2The content is 15vol.%, the inlet gas pressure is regulated to be 1-5 bar, the inlet gas flow rate is 100-120 mL/min < -1 >, the temperature of an adsorption column is 25-75 ℃, and downstream gas components are monitored on line through a gas infrared analyzer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113926304A (en) * | 2021-03-22 | 2022-01-14 | 青岛大学 | Low-temperature demercuration adsorbent for coal-fired flue gas |
| CN114797784A (en) * | 2022-05-10 | 2022-07-29 | 太原理工大学 | System and method for preparing and recycling functional MOFs-based flue gas pollutant adsorbent by utilizing production environment of coal-fired power plant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113926304A (en) * | 2021-03-22 | 2022-01-14 | 青岛大学 | Low-temperature demercuration adsorbent for coal-fired flue gas |
| CN113926304B (en) * | 2021-03-22 | 2024-01-16 | 青岛大学 | Low-temperature mercury-removing adsorbent for coal-fired flue gas |
| CN114797784A (en) * | 2022-05-10 | 2022-07-29 | 太原理工大学 | System and method for preparing and recycling functional MOFs-based flue gas pollutant adsorbent by utilizing production environment of coal-fired power plant |
| CN114797784B (en) * | 2022-05-10 | 2023-05-05 | 太原理工大学 | System and method for preparing and recycling functionalized MOFs-based flue gas pollutant adsorbent by using coal-fired power plant production environment |
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