CN114225910B - Amination modified Co-MOFs material with NO adsorption separation performance - Google Patents
Amination modified Co-MOFs material with NO adsorption separation performance Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000000926 separation method Methods 0.000 title claims abstract description 12
- 238000005576 amination reaction Methods 0.000 title claims abstract description 7
- 239000012921 cobalt-based metal-organic framework Substances 0.000 title abstract description 5
- 239000013118 MOF-74-type framework Substances 0.000 claims abstract description 63
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003546 flue gas Substances 0.000 claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
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- 239000002086 nanomaterial Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 128
- 238000000034 method Methods 0.000 description 11
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- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
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Classifications
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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
- 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]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
The invention discloses an amination modified Co-MOFs material with NO adsorption separation performance, which is characterized in that MOF-74 metal-organic framework material is used as a carrier to prepare a material containing amino active sites, and the obtained NH 2 The original crystal structure and pore canal are reserved in the MOF-74 composite material, and the nano material is a novel adsorption material capable of adsorbing and separating NO in flue gas.
Description
Technical Field
The invention relates to a method for preparing amination (-NH) by using metal organic framework material 2 ) The material for modifying active site, in particular to a method for preparing NH with amino modified active site and high stability by taking Co-MOF-74 metal organic framework material as carrier 2 The MOF-74 composite material has higher NO adsorption capacity and adsorption selectivity, and can be suitable for the NO adsorption separation purification and the recycling of atmospheric pollutants in mixed gas.
Background
In recent years, the national requirements for denitration and emission reduction of chemical enterprises are more and more strict, the industrial kiln uses coal as fuel, and the discharged flue gas contains a large amount of sulfur oxides, suspended particles, carbon monoxide, unburned complete hydrocarbon and nitrogen oxides. Among them, the most serious hazard of nitrogen oxides is considered as a major pollutant of the atmosphere. The current research discovers that the discharged flue gas of the thermal power plant has the characteristics of large flue gas quantity and continuous discharge. The metal smelting industry uses a large amount of nitric acid in the processes of acid washing, acid dissolution and leaching, and the generated flue gas has the characteristics of high sodium concentration and intermittent discharge. The existing pin removal technology can be divided into catalytic reduction, liquid absorption method and adsorbent absorption methodAnd (5) waiting for a furnace. At present, the treatment method of nitrogen oxides in the production process of enterprises mainly comprises selective catalytic reduction, and the method has the problems of high investment cost, low catalyst poisoning and low removal efficiency of low-concentration nitrogen oxides (DOI: 10.1016/j.jre.2017.06.004). The adsorbent is used for treating the flue gas, so that the high-concentration nitrogen oxides can be directly adsorbed, and then released through a heating or depressurizing method to be recycled, and the low-concentration nitrogen oxides can be recycled. To achieve the adsorption of nitrogen oxides, an adsorbent with good selectivity and large adsorption capacity is needed. It has been reported that MFM-520, MOFs metal-organic framework materials (metal nodes are divalent Zn ions, organic ligands are 4, 4-bipyridine-3, 3', 5' -tetracarboxylic acid salts) can realize NO 2 High-efficient adsorption of NO at 298K and 1kPa 2 The adsorption quantity reaches 4.2 mmol.g -1 For CO 2 IAST theory selectivity of up to 675, while adsorbing NO 2 Quantitative conversion to HNO 3 (DOI:10.1038/s41557-019-0356-0)。
But more than 90% of Nitrogen Oxides (NO) x ) The NO component exists, and the development of the high-efficiency NO adsorption separation material has great engineering significance. Oxide as carrier for loading noble metal to NO x Catalytic denitration of contaminants shows excellent performance (penguin, etc. noble metals 2002,23 (2): 6-10), but metal oxides tend to agglomerate during use as adsorbents, resulting in reduced application performance. HKUST-1MOFs material containing unsaturated metal site Cu can reach NO adsorption capacity of 3 mmol.g under normal temperature and pressure -1 (DOI: 10.1021/ja066098 k); the adsorption capacity of CPO-27-Ni and CPO-27-Co MOFs material to pure NO can reach 6-7 mmol.g -1 (DOI: 10.1021/cm800686 k); IRMOF-3 and UMCM-1-NH after amine functionalization 2 MOFs material has the adsorption capacity of 6.4 mmol.g to NO -1 And 1.67 mmol.g -1 (DOI: 10.1039/c000154 f). The material is mainly aimed at storing and adsorbing NO gas molecules with higher purity, such as biomedical NO gas, and has unknown selectivity under mixed atmosphere.
Co-adsorption characteristic Density Functional Theory (DFT) calculation under mixed atmosphere shows that the adsorption amount of NO reaches the maximum when the adsorption pressure of Cu-BTC is 5atm at normal temperatureBig (10 mmol.g) -1 ) CO at an adsorption pressure of 50atm 2 The adsorption capacity reaches the maximum (21 mmol.g) -1 ) When the adsorption pressure increases, more CO than NO is present 2 Is adsorbed by Cu-BTC, and the adsorption selectivity of NO is poor (DOI: 10.1016/j. Cap.2015.06.011). Taken together, MOFs materials have initially demonstrated excellent NO x The adsorption storage performance, but the existing research mainly aims at storing and adsorbing NO gas molecules with higher purity, such as biomedical NO gas, and has limited selectivity in competitive adsorption with other gases. From the engineering application point of view, for atmospheric pollutants NO in complex atmospheres x The adsorption selectivity and the adsorption capacity are important.
In view of the above, the invention selects the organic metal framework material to introduce the amino group into the MOF-74 material to prepare the material with amino group modification so as to improve the NO adsorption performance and the adsorption selectivity, thus being an amination modified Co-MOFs material with NO adsorption separation performance.
Disclosure of Invention
The invention aims to prepare NH with amino modified active site and high stability by taking MOF-74 metal organic framework material as a carrier 2 -MOF-74, the NH obtained 2 The MOF-74 composite material can be used as a potential nano adsorption material for adsorbing and separating NO in flue gas.
The invention provides an amination modified Co-MOFs material with NO adsorption separation performance, which is prepared by the following steps:
(1) Cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O), 2, 5-dihydroxyterephthalic acid (DOBDC), N-Dimethylformamide (DMF) and methanol are put into a polytetrafluoroethylene liner of a reaction kettle, stirred until the solid is completely dissolved, and the liner is put into a vacuum drying oven for vacuum degassing for 30-60 minutes at room temperature. Wherein DOBDC and Co (NO 3 ) 2 ·6H 2 The feeding mole ratio of O is 1:3.3, and the mass ratio of the volume usage of DMF and methanol to the cobalt nitrate hexahydrate is 50-60 mL:10mL:1g.
(2) Placing the reaction kettle in the step (1) in an incubator to react for 36 hours at 80-100 ℃, and then reducing the temperature to room temperature by a program to reversely reactAnd taking out the kettle. Wherein, the program heating and cooling rates are 2 ℃/min. The resultant was taken out and washed three times with DMF by ultrasonic treatment, and after removal of DMF by centrifugation, methanol (CH) 3 OH), soaking for 3d (methanol change every 12 h) to remove residual unreacted material. And centrifugally removing methanol, and then placing the synthesized product into a blast drying oven to be dried for 6-8 hours at the temperature of 100-120 ℃ to obtain reddish brown MOF-74 crystals. Wherein, the volume consumption of DMF and the volume consumption of methanol for each washing are one third of the volume consumption of DMF in the synthesis reaction.
(3) Taking the MOF-74 synthesized in the step (2), adding Monoethanolamine (MEA) and methanol, mixing, putting into a polytetrafluoroethylene liner of a reaction kettle, carrying out ultrasonic oscillation at 25 ℃ for 20-30 minutes, putting the liner into a vacuum drying oven, carrying out vacuum degassing at room temperature for 30-60 minutes, and putting the reaction kettle into a constant temperature oven for reacting for 20 hours at 100-120 ℃, wherein the program heating and cooling rates are 2 ℃/min. Soaking the separated product in methanol for 24 hr (replacing methanol every 12 hr), centrifuging, drying the separated product at 100-120deg.C for 6-8 hr to obtain modified NH 2 -MOF-74 powder. Wherein the mass ratio of the monoethanolamine to the methanol to the MOF-74 is 5mL: 40-50 mL/1 g.
(4) NH obtained in step (3) 2 Placing MOF-74 powder in vacuum drying oven, drying at 100deg.C for more than 12 hr to obtain fully activated NH 2 -MOF-74 material. The material is applied to NO adsorption separation.
Drawings
FIG. 1 is the NH obtained in the examples 2 XRD crystal phase Structure of MOF-74.
FIG. 2 is the NH obtained in the example 2 TG thermal stability profile of MOF-74.
FIG. 3 is the NH obtained in the example 2 High definition SEM topography of MOF-74.
FIG. 4 is the NH obtained in the example 2 Specific surface area and pore size distribution of MOF-74.
FIG. 5 is the NH obtained in the example 2 Isothermal adsorption performance profile of MOF-74.
FIG. 6 is the NH obtained in the example 2 -NO adsorption cycle performance profile of MOF-74.
FIG. 7 is the NH obtained in the example 2 -MOAdsorption penetration curve in the mixed atmosphere of F-74.
Detailed Description
The present invention will be described in detail with reference to the following examples.
Example 1
(1) Raw materials
Cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) and 2, 5-dihydroxyterephthalic acid (DOBDC) are both analytically pure; n, N-Dimethylformamide (DMF), monoethanolamine (MEA) and methanol (CH) 3 OH) was chemically pure (99%).
(2) MOF-74 Synthesis
Solvothermal synthesis of MOF-74: 1.2g (4.12 mmol) of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O, AR), 0.2702g (1.37 mmol) of 2, 5-dihydroxyterephthalic acid (DOBDC, AR), and 50mL of N, N-Dimethylformamide (DMF) were mixed into a 100mL polytetrafluoroethylene liner and stirred until the solids were completely dissolved and the solution was pink. Placing the liner into a vacuum drying box, vacuum degassing at room temperature for 30 min, taking out, placing the reaction kettle into an electrothermal constant temperature blast drying box, reacting at 80deg.C for 36 hr at 3 deg.C for min -1 And (5) cooling. After removal, 20mL of DMF was added and the mixture was sonicated three times and centrifuged, and then 20mL of methanol (CH) 3 OH) was soaked for 3 days (replacement of solution every 12 h) to remove residual impurities. After removing the methanol, the mixture is put into a 100 ℃ oven for drying for 6 hours, and the reddish brown MOF-74 crystals are obtained.
(3) NH of amino modified active site 2 Preparation of the-MOF-74 Material
Taking 1g of MOF-74 synthesized in the step (2), adding 5mL of Monoethanolamine (MEA) and 40mL of methanol, mixing, placing into a polytetrafluoroethylene liner of a reaction kettle, carrying out ultrasonic oscillation at 25 ℃ for 20-30 minutes, placing the liner into a vacuum drying oven, carrying out vacuum degassing at room temperature for 30 minutes, and placing the reaction kettle into a constant temperature oven for reaction at 120 ℃ for 20 hours, wherein the program heating and cooling rates are 2 ℃/min. Soaking the separated product in methanol for 24 hr (replacing methanol every 12 hr), centrifuging, and drying at 100deg.C for 6 hr to obtain modified NH 2 -MOF-74 powder.
(4)NH 2 -MOF-74 material activation
NH obtained in step (3) 2 Placing MOF-74 powder in vacuum drying oven, drying at 100deg.C for more than 12 hr to obtain fully activated NH 2 -MOF-74 material. The material is applied to NO adsorption separation.
(5) Characterization of materials
NH obtained in the step (4) 2 -MOF-74 material in X' Pert 3 The Powder type multifunctional X-ray diffractometer (Panake, netherlands) tests the crystal phase structure (PXRD), the U.S. SDT-Q600 type synchronous TGA/DSC analyzer to characterize the thermal stability, the Hitachi high new thermal field emission scanning electron microscope SU5000 to characterize the material morphology, the specific surface area and the pore size of the physical adsorption instrument SSA-7000 of Piaode electronic technology Co., ltd. And the results are shown in the accompanying drawing 1, the accompanying drawing 2, the accompanying drawing 3 and the accompanying drawing 4 of the specification respectively.
(6) NO adsorption separation Performance test
The isothermal adsorption line of NO in the sample at 0-100 KPa was measured by physical adsorption apparatus of Piaode instruments Co., ltd under 293K, and the result is shown in FIG. 5. Simultaneously, the material is subjected to degassing treatment under the vacuum at 140 ℃, and then is subjected to adsorption cyclicity test by a physical adsorption instrument, and the result is shown in figure 6
Adsorption breakthrough curves under mixed atmosphere simulated flue gas NO, CO was tested using DECRA quantitative gas analysis mass spectrometer from Hiden, england 2 、O 2 The concentration of the mixture. The U-shaped quartz hollow tube is introduced with N under the 293K condition 2 Purging other gases in the reaction tube, and bypassing and introducing 10 mL/min -1 Mixed gas (1000 ppm NO, 1000ppm O) 2 、2000ppm CO 2 Residual air N 2 ) After the mass spectrum detection baseline is stable, the mixed gas is switched into a reaction tube, and a mass spectrometer signal is recorded. With 0.1g NH 2 The MOF-74 sample is placed in a U-shaped quartz reaction tube, the signals of a mass spectrometer are recorded in the same method, and the absorption penetration curve of the sample is obtained after the signals of the empty tube are compared. The results are shown in FIG. 7 and Table 2.
(7) Example results analysis
The crystalline phase Structure (PXRD) of the MOF-74 material obtained from the example synthesis (FIG. 1) shows that NH 2 The diffraction characteristic peaks of MOF-74 are consistent with those of MOF-74, indicating that the material is still a framework structure characteristic of MOF-74. Drawings2 shows NH 2 -MOF-74 and MOF-74 TG heat stability weightlessness curve trend basically consistent, amino modified NH 2 The MOF-74 material gradually decomposes and collapses at 310-450 ℃, which shows that the thermal stability of the material is above 330 ℃ and is good. The flue gas temperature of the industrial kiln gas in the non-power plant industry after desulfurization is lower than 100 ℃. Thus, the material may be suitable for applications in a flue gas environment.
FIG. 3 shows MOF-74 and NH 2 The morphology structure of the MOF-74 is an elongated rod-shaped crystal, and a one-dimensional pore canal structure exists, so that the MOF-74 has larger specific surface area and porosity and is NH 2 The adsorption separation of NO by MOF-74 provides a basis and a modification site, and the crystal structure is still complete after modification of amino groups.
FIG. 4 and Table 1 show that MOF-74 and NH 2 N of-MOF-74 2 The adsorption-desorption curves are basically consistent, the adsorption curves are typical I-type adsorption isotherms, and the adsorption curves show that the structure of the material is not greatly changed after the amino group is introduced, the material is still mainly provided with micropores, and the pore channel of the material is smaller than that of the material modified by the amino group.
FIG. 5 shows that MOF-74 has an adsorption of 149.3cc/g of NO and NH at 100KPa 2 -MOF-74 of 189.3cc g -1 The comparative MOF-74 increased by about 26.8% and exhibited stronger adsorption performance under low pressure conditions.
FIG. 6 shows that the material saturated with NO is subjected to vacuum heating treatment and then subjected to adsorption test again, and NH is circulated for 4 times 2 The regeneration performance of the MOF-74 for adsorbing NO is shown in FIG. 7. From the figure, NH at first cycle 2 The adsorption amount of NO by the-MOF-74 is 189.663 cc.g -1 No. 2 cycle test shows that the amount of adsorbed NO is 185.66 cc.g -1 No. 3 cycle test shows that the amount of adsorbed NO is 179.34 cc.g -1 No. 4 cycle test shows that the amount of adsorbed NO is 180.01 cc.g -1 . In the adsorption-desorption process, NH 2 NO significant decrease in the adsorption of NO by MOF-74, indicating NH 2 The MOF-74 can keep higher stability in the NO adsorption-desorption process, and the material has excellent regeneration performance and can be applied to the field of NO recycling.
FIG. 7 and Table 2 show that under simulated mixed atmospheresFurther testing the adsorption performance of the material by the adsorption penetration curve of (2), simulating NH under the flue gas atmosphere 2 The NO saturation adsorption capacity of the-MOF-74 material was 116.6 cc.g -1 Is O 2 Adsorption amount of 8 times, NO to CO under mixed atmosphere 2 The adsorption selectivity of (2) was about 4.14.
In conclusion, the results of the examples show that the invention uses MOF-74 metal organic framework material as a carrier to prepare the nano porous material with amino modified active site and high stability, and the adsorption performance is stable after multiple cycles. NH containing an amino modified active site 2 The MOF-74 material greatly improves and promotes the NO adsorption capacity and the adsorption selectivity of the MOFs material, the NO adsorption performance is remarkably improved, and the method has better purification and recycling application potential of atmospheric pollutant NO. NH obtained by the invention 2 The MOF-74 material can be used as a potential adsorbing material for adsorbing and separating NO in flue gas.
TABLE 1 MOF-74 and NH 2 Specific surface area and pore size of MOF-74
TABLE 2 NH 2 Adsorption amount under MOF-74 mixed atmosphere
Claims (1)
1. Amination modified NH 2 Application of MOF-74 material in adsorbing and separating NO in flue gas, and preparation of NH with amino modified active site by taking Co-MOF-74 metal organic framework material as carrier 2 The specific steps of the-MOF-74 composite material are as follows:
(1) Co-MOF-74 synthesized by a reaction system of cobalt nitrate hexahydrate, 2, 5-dihydroxyterephthalic acid, N-dimethylformamide and methanol under a solvothermal method is added with monoethanolamine and methanol, mixed and placed into a polytetrafluoroethylene liner of a reaction kettle, ultrasonic oscillation is carried out for 20-30 minutes at 25 ℃, and then the liner is placed into vacuumVacuum degassing is carried out for 30-60 minutes at room temperature in a drying oven, then the reaction kettle is placed in a constant temperature oven for reacting for 20 hours at 100-120 ℃, wherein the program heating and cooling rates are 2 ℃/min; soaking the separated solid phase product in methanol for 24 hr, replacing methanol for 12 hr, and centrifuging; drying the separated solid phase product at 100-120 deg.c for 6-8 hr to obtain modified NH 2 -MOF-74 powder; wherein the dosage ratio of the monoethanolamine to the methanol to the MOF-74 is 5 mL:40-50 mL:1g;
(2) NH obtained in step (1) 2 Placing MOF-74 powder in vacuum drying oven, drying at 100deg.C for more than 12 hr to obtain fully activated NH 2 -MOF-74 material and application in the adsorption separation of NO in flue gas.
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