CN113354829A - Zeolite imidazolate framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]Preparation and use of - Google Patents
Zeolite imidazolate framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]Preparation and use of Download PDFInfo
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Abstract
The invention discloses a zeolite imidazolate framework material CHA- [ Zn (2-mIm) with a CHA topological structurex(mbIm)2‑x]The preparation method and the application thereof. CHA- [ Zn (2-mIm) with different chemical compositions, BET specific surface area and cage diameter is synthesized by changing the feeding molar ratio of two ligandsx(5‑mbIm)2‑x](x =0.70 ± 0.02 and x =0.83 ± 0.03) material. The present invention provides CHA- [ Zn (2-mIm)x(5‑mbIm)2‑x](x =0.70 ± 0.02) preferentially adsorbs acetone with a short molecular chain, so that steric hindrance separation of acetone and butanol can be realized; CHA- [ Zn (2-mIm)x(5‑mbIm)2‑x](x =0.83 ± 0.03) preferentially adsorbs butanol, enabling thermodynamic separation of butanolone.
Description
Technical Field
The invention relates to a zeolite imidazolate framework material CHA- [ Zn (2-mIm) with CHA topologyx(mbIm)2-x]The preparation method and the application thereof in the aspect of adsorption separation. In particular to a method for preparing a drug by regulating 2-methylimidazole (2-mIm) and 5(6) -methylbenzimidazole (mbIm) in CHA- [ Zn (2-mIm)x(mbIm)2-x]By changing the molar ratio ofCage diameter, thereby realizing the technology of separating butanol and acetone. Belongs to the field of inorganic functional material application.
Background
With the shortage of petroleum resources and the aggravation of environmental problems, the advantages of biofuels are increasingly highlighted. The biobutanol produced by ABE (acetone-butanol-ethanol) fermentation method is a potential biofuel due to high energy density and octane number, high calorific value and high mixing property. However, in the production of butanol by ABE fermentation, a low-concentration mixed aqueous solution containing ethanol, acetone and butanol is obtained, which causes difficulty in the separation of biobutanol. The adsorption separation method is suitable for a multi-component system which is difficult to separate by the traditional separation technology because of low energy consumption and high selectivity of the process.
Zeolite imidazolate framework materials (ZIFs) have the advantages of large pore volume and high specific surface area, and the pore channel configuration and the pore surface property of the ZIFs can be regulated and controlled by changing the groups of imidazole ligands, so that the selectivity of multi-component substances can be effectively improved.
The synthesis of ZIF-302 materials with zeolite CHA topology (Nguyen N T, Furukawa H, G a ndra F, et al. Selective capture of carbon dioxide units and intermediates by hydrolytic catalyst-type zeolite structures [ J.sub.J. ], has been carried out by researchers using divalent metal Zn salts, 2-methylimidazole (2-mIm) and 5(6) -methylbenzimidazole (mbIm)]Angewandte Chemie, 2014, 126(40): 10821-10824) and investigated its hydrophilicity and hydrophobicity and its ability to CO2/N2The adsorption separation performance of (1). The synthesis method of ZIF-302 in the study is as follows: according to the divalent metal Zn salt: 2-methylimidazole (2-mIm): (5) (6) -Methylbenzimidazole (mbIm) = 1.0: 0.86: 1.0 on a molar basis, the above materials were sequentially added to a mixed solvent of N, N-dimethylformamide and water (19: 1 by volume) at room temperature, and the mixture was reacted at 120 ℃ to obtain a ZIF-302 material having a BET of 240 m measured by Ar2(ii) in terms of/g. However, there is no report in the literature that CHA- [ Zn (2-mIm) can be changed by adjusting the molar ratio of 2-methylimidazole (2-mIm) to 5(6) -methylbenzimidazole (mbIm) ligandsx(mbIm)2-x]BE for materialT and pore structure. We therefore wish to modify CHA- [ Zn (2-mIm) by adjusting the molar ratio of the two imidazole ligands mentioned abovex(mbIm)2-x]The BET and cage structure of the material expand the application of the material in the aspect of adsorption separation of low-concentration butanol and acetone mixed aqueous solution.
Disclosure of Invention
The invention aims to provide a zeolite imidazole ester framework material CHA- [ Zn (2-mIm) with a CHA topological structurex(mbIm)2-x]And provides the application of the adsorbent in the aspect of adsorbing and separating the mixed aqueous solution of the butanol and the acetone with low concentration.
The invention provides a zeolite imidazole ester framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]Has an elliptical cage-like structure and has strong affinity to small molecule adsorbates. Since the butanol molecules are significantly larger in size than the acetone molecules, it is possible to modulate CHA- [ Zn (2-mIm)x(mbIm)2-x]The molar ratio of 2-methylimidazole to 5(6) -methylbenzimidazole ligand in the material changes the size of the cage diameter of the material, and the separation of butanol and acetone is realized. Wherein, CHA- [ Zn (2-mIm) is obtained after adjustmentx(5-mbIm)2-x](x =0.70 ± 0.02) enabling steric separation of acetone/butanol; CHA- [ Zn (2-mIm)x(5-mbIm)2-x](x =0.83 ± 0.03) enables thermodynamic separation of butanol/acetone.
The invention provides a zeolite imidazole ester framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]The preparation method comprises the following steps:
(1) mixing and stirring 87.5mL of N, N-dimethylformamide and 12.5mL of deionized water uniformly at room temperature to form a solution A, and dividing the solution A into two parts;
(2) the raw materials for synthesis are zinc nitrate hexahydrate, 2-methylimidazole (2-mIm) and 5(6) -methylbenzimidazole (mbIm);
dissolving zinc nitrate hexahydrate (4.48 mmol, 1.33 g) in one portion of the solution A, and stirring uniformly to form a solution B;
respectively dissolving 2-methylimidazole (2-mIm) and 5(6) -methylbenzimidazole (mbIm) in the other part of solution A, and uniformly mixing to form solution C;
the molar ratio of the 2-methylimidazole to the 5(6) -methylbenzimidazole is 0.75-1.25: 1.25 or 3.0-4.0: 1.25;
(3) transferring the solution C into a reaction kettle, and slowly adding the solution B into the reaction kettle; reacting for 3-5 days at 100-120 ℃;
(4) after the reaction kettle is cooled, the obtained sample is washed for a plurality of times by ethanol, filtered and dried at room temperature to obtain the zeolite imidazole ester framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]。
(5) CHA- [ Zn (2-mIm) obtained by liquid nuclear magnetic analysis when the synthesis molar ratio of 2-methylimidazole (2-mIm) in the raw material mixture ratio is 0.75-1.25x(mbIm)2-x]Has a chemical composition of x =0.70 ± 0.02; CHA- [ Zn (2-mIm) obtained by liquid nuclear magnetic analysis when the synthesis molar ratio of 2-methylimidazole (2-mIm) in the raw material mixture ratio is 3.0-4.0x(mbIm)2-x]Has a chemical composition of x =0.83 ± 0.03.
The invention provides a zeolite imidazole ester framework material CHA- [ Zn (2-mIm) prepared by the methodx(mbIm)2-x]The application of butanol and acetone in adsorption separation of mixed water solution is provided.
The present invention provides CHA- [ Zn (2-mIm)x(mbIm)2-x]The material is applied to the adsorption separation of butanol and acetone in ABE fermentation liquor, and finally butanol aqueous solution or acetone aqueous solution is obtained. The adsorption separation performance test method adopts a static adsorption experiment or a dynamic column adsorption experiment, wherein in the static adsorption experiment, the concentration range of butanol is as follows: 0.2-20 g L-1(ii) a The concentration range of acetone is: 0.2-20 g L-1(ii) a In dynamic column adsorption experiment, the concentration range of butanol in the mixed aqueous solution is 10-20g L-1The concentration range of the acetone is 10-20g L-1。
The static adsorption experiment described above in the application was operated as follows: CHA- [ Zn (2-mIm)x(mbIm)2-x]The material is activated for 36 h by methanol at room temperature, then prepared into particles of 500-600 mu m, and is activated for 12 h by vacuum pumping at 150 ℃ to remove guest molecules; weighing 0.05-0.1 g adsorbent particles into a 10 mL centrifuge tube, adding 5mL butanol/acetone (0.2-20 g L) with different concentrations-1/0.2-20 g L-1) And (3) standing the mixed solution for 24 h in an environment at 25 ℃ to ensure that adsorption saturation is achieved. The samples were then centrifuged, the supernatant filtered and the concentration quantified in a gas chromatograph.
The dynamic column adsorption experiment described above was operated as follows: CHA- [ Zn (2-mIm)x(mbIm)2-x]The material is activated for 36 h by methanol at room temperature, then prepared into particles with the particle size of 500-600 μm, and is activated for 12 h by vacuum pumping at 150 ℃ to remove guest molecules; then the adsorbent particles were packed in a stainless steel packed column (phi 6mm, 27 cm) with quartz wool at both ends and a packing layer height of 25 cm. Respectively mixing butanol/acetone mixed solution at 25 deg.C with high pressure injection pump, wherein the concentration of butanol in the mixed solution is 10-20g L-1The concentration range of the acetone is 10-20g L-1At a rate of 0.05-0.1 mL min-1The flow rate of the mixed solution flows through the packing layer from bottom to top, then a 2 mL chromatographic bottle is used for receiving effluent at the outlet end, a sample is collected every 10 min, and the concentration of the sample is quantitatively analyzed through gas chromatography.
The invention has the beneficial effects that:
(1) compared with the reported ZIF-302 material, the CHA- [ Zn (2-mIm)x(mbIm)2-x]The material changes with the raw material molar ratio to obtain CHA- [ Zn (2-mIm) with different chemical composition, BET and cage diameterx(5-mbIm)2-x](x =0.70 ± 0.02 or x =0.83 ± 0.03).
(2) The present invention provides CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.70 ± 0.02) material having a cage diameter of 5.5 a capable of effecting steric separation of acetone/butanol; CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.83 ± 0.03) material having a cage diameter of 8.1 a capable of achieving thermodynamic separation of butanol/acetone.
Drawings
FIG. 1 shows CHA- [ Zn (2-mIm) synthesized in example 1x(mbIm)2-x]Powder X-ray diffraction (PXRD) pattern of the material (X =0.70 ± 0.02 and X =0.83 ± 0.03).
FIG. 2 shows CHA- [ Zn (2-mIm) in example 2x(mbIm)2-x](x =0.70 ± 0.02 and x =0.83 ± 0.03) Ar adsorption desorption curve at 77K and Ar pore size distribution plot.
FIG. 3 shows CHA- [ Zn (2-mIm) in example 2x(mbIm)2-x](x =0.70 ± 0.02 and x =0.83 ± 0.03) CO at 273K2Adsorption Curve and CO2The aperture profile.
FIG. 4 shows CHA- [ Zn (2-mIm) in example 3x(mbIm)2-x](x =0.70 ± 0.02 and x =0.83 ± 0.03) static adsorption curves for single components acetone and butanol.
FIG. 5 shows CHA- [ Zn (2-mIm) in example 4x(mbIm)2-x](x =0.70 ± 0.02) two-component dynamic column adsorption profile to butanol/acetone.
FIG. 6 shows CHA- [ Zn (2-mIm) in example 5x(mbIm)2-x](x =0.83 ± 0.03) two-component dynamic column adsorption profile to butanol/acetone.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1: CHA- [ Zn (2-mIm)x(mbIm)2-x]Synthesis of (2)
CHA-[Zn(2-mIm)x(mbIm)2-x]The synthesis steps are as follows: the method is synthesized according to the raw material molar ratio of zinc nitrate hexahydrate (99.0%, national drug group chemical reagent limited): 2-methylimidazole (98.0%, alatin reagent (shanghai) limited): 5(6) -methylbenzimidazole (98.0%, pee medicine technology limited) = 1.0: 1.75-1.25/3.0-4.0): 1.25, and comprises the following specific steps:
(1) mixing and stirring 87.5mL of N, N-dimethylformamide and 12.5mL of deionized water uniformly at room temperature to form a solution A, and dividing the solution A into two parts;
(2) dissolving zinc nitrate hexahydrate (4.48 mmol, 1.33 g) in one portion of the solution A, and stirring uniformly to form a solution B; mixing 2-methylimidazole (2-mIm) and 5-methylbenzimidazole in a molar ratio of 0.75-1.25: 1.25 and 3.0 to 4.0: 1.25 are respectively dissolved in the other part of the solution A and are uniformly mixed to form a solution C;
(3) transferring the solution C into a reaction kettle, and slowly adding the solution B into the reaction kettle; reacting for 3-5 days at 100-120 ℃;
(4) after the reaction kettle is cooled, the obtained sample is washed for a plurality of times by ethanol, filtered and dried at room temperature to obtain the zeolite imidazole ester framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]。
(5) CHA- [ Zn (2-mIm) obtained by liquid nuclear magnetic analysis when the synthesis molar ratio of 2-methylimidazole (2-mIm) in the raw material mixture ratio is 0.75-1.25x(mbIm)2-x]Has a chemical composition of x =0.70 ± 0.02; CHA- [ Zn (2-mIm) obtained by liquid nuclear magnetic analysis when the synthesis molar ratio of 2-methylimidazole (2-mIm) in the raw material mixture ratio is 3.0-4.0x(mbIm)2-x]Has a chemical composition of x =0.83 ± 0.03.
The phase structure of the obtained product is determined by PXRD. FIG. 1 shows two CHA- [ Zn (2-mIm) synthesized with different chemical compositionsx(mbIm)2-x]The diffraction pattern of (a). By comparison, it was found that synthesized CHA- [ Zn (2-mIm)x(mbIm)2-x]The diffraction peak angle of the crystal is completely consistent with the diffraction peak angle simulated by the corresponding structure, no impurity peak exists, and the crystallinity is high.
Example 2: CHA- [ Zn (2-mIm)x(mbIm)2-x]Pore size analysis of
As shown in FIGS. 2 and 3, CHA- [ Zn (2-mIm) was measured at 77K and 293K temperatures, respectivelyx(mbIm)2-x]Ar adsorption desorption isotherm and CO of material2Adsorption isotherms. Calculating CHA- [ Zn (2-mIm)x(mbIm)2-x]BET of (x = 0.70. + -. 0.02 and x = 0.83. + -. 0.03) is 100. + -. 25m, respectively2The sum of the amounts of the components is 600 +/-25 m2(ii)/g; the cage diameters are 5.5A and 8.1A respectively.
Example 3: single component static adsorption experiment
This example uses CHA- [ Zn (2-mIm) prepared in example 1x(mbIm)2-x](x =0.70 ± 0.02 and x =0.83 ± 0.03) static adsorption experiments were performed. Before the experiment, a sample is activated for 36 h by using methanol at room temperature, then prepared into particles of 500-. Single component butanol (0.2-20 g L)-1) And acetone (0.2-20 g L)-1) The static adsorption experiment was performed as follows: 0.1 g of the adsorbent particles were weighed into a 10 mL centrifuge tube and 5mL of butanol (0.2-20 g L) at different concentrations were added-1) And acetone (0.2-20 g L)-1) The solution was then sealed and left to stand in a 25 ℃ environment for 24 h to ensure that adsorption saturation was reached. After adsorption, the sample was centrifuged, the supernatant was filtered through a membrane, and the concentration was analyzed by gas chromatography.
FIG. 3(a) shows CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.70 ± 0.02) and CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.83 ± 0.03) static adsorption isotherm of two materials for acetone. The results showed that the maximum adsorption amounts of acetone and acetone were 111.4 mg g-1And 136.2 mg g-1. FIG. 3(b) shows CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.70 ± 0.02 and x =0.83 ± 0.03) static adsorption isotherm for butanol. CHA- [ Zn (2-mIm) with smaller cage diameterx(mbIm)2-x](x =0.70 ± 0.02) the adsorption amount of butanol was only 64.5 mg g-1(ii) a CHA- [ Zn (2-mIm) with larger cage diameterx(mbIm)2-x](x =0.83 +/-0.03) can reach the adsorption capacity of 152.8 mg g for butanol-1。
Example 4: CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.70 ± 0.02) two-component dynamic column adsorption experiment
This example uses CHA- [ Zn (2-mIm) prepared in example 1x(mbIm)2-x](x =0.70 ± 0.02 and x =0.83 ± 0.03) two-component dynamic column adsorption experiments were performed. Before the experiment, the adsorbent is activated for 36 h by methanol at room temperature, then prepared into 500-acetone 600 mu m particles, then vacuumized and activated for 12 h at 150 ℃ to remove solvent molecules, and then the pipelines are rinsed by a bi-component butanol/acetone mixed solution to ensure that the solution concentration is uniform; filling the adsorbent particles into a stainless steel packed column, wherein quartz wool is filled at two ends of the column, and the height of a packing layer is 25 cm; at the environmental temperature of 25 ℃, a high-pressure injection pump is used for mixing the two-component butanol/acetone mixed solution for 0.05 mL min-1The flow rate of the liquid flows through the packing layer from bottom to top, the discharge liquid is connected at the outlet end, and 2 mL chromatographic vials are used for every 10 minA0.5 mL sample was collected and analyzed for concentration by gas chromatography.
FIG. 5(a) shows CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.70 ± 0.02) to two-component butanol/acetone (20 g L)-1/10 g L-1) The breakthrough column adsorption curve of (1). The results show that: in the two-component butanol/acetone (20 g L)-1/10 g L-1) In the mixed solution of (1), CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.70 ± 0.02) dynamic adsorption amount of butanol of only 44.5 mg g-1(ii) a And the dynamic adsorption capacity to acetone was 71.8 mg g-1Significantly greater than the dynamic adsorption capacity of butanol. The dynamic selectivity of the acetone/butanol is calculated to reach 3.2, because the butanol molecules are limited by the cage diameter of the material and can hardly enter the pore channels, and finally, the steric separation of the acetone and the butanol is realized. FIG. 5(b) shows CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.70 ± 0.02) to two-component butanol/acetone (10 g L)-1/10 g L-1) The breakthrough column adsorption curve of (1). With the two components butanol/acetone (20 g L)-1/10 g L-1) The penetration ratio of (1): when the butanol concentration decreased, the adsorption capacity of butanol decreased, and the final adsorption amount was 39.7 mg g-1(ii) a While the adsorption amount of acetone was increased to 82.1 mg g-1。
Example 5: CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.83 ± 0.03) two-component dynamic column adsorption experiment
This example uses the CHA- [ Zn (2-mIm) synthesized in example 1x(mbIm)2-x](x =0.83 ± 0.03) two-component dynamic column adsorption experiments were performed. Before the experiment, the adsorbent material is activated for 36 h by methanol at room temperature, then prepared into 500-acetone 600-micron particles, then vacuumized and activated for 12 h at 150 ℃ to remove solvent molecules, and then the pipelines are rinsed by a bi-component butanol/acetone mixed solution to ensure that the solution concentration is uniform; filling the adsorbent particles into a stainless steel packed column, wherein quartz wool is filled at two ends of the column, and the height of a packing layer is 25 cm; at the environmental temperature of 25 ℃, a high-pressure injection pump is used for mixing the two-component butanol/acetone mixed solution for 0.05 mL min-1The flow velocity of the water flows through the packing layer from bottom to top and is connected with the outlet endThe effluent was collected into a 2 mL chromatography vial at intervals of 10 min to obtain 0.5 mL samples, and the concentrations of the samples were quantitatively analyzed by gas chromatography.
FIG. 6(a) shows the adsorbent versus two-component butanol/acetone (20 g L)-1/10 g L-1) The breakthrough column adsorption curve of (1). The results show that: in butanol/acetone (20 g L)-1/10 g L-1) In the mixture of (1), CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.83 ± 0.03) adsorption capacity for butanol of 142.8 mg g-1(ii) a While the acetone is replaced, the adsorption quantity of the acetone in the final balance is 34.2 mg g-1At this time, the dynamic selectivity of butanol/acetone was 2.0, and thermodynamic separation between acetone/butanol was achieved.
FIG. 6(b) shows CHA- [ Zn (2-mIm)x(mbIm)2-x](x =0.83 ± 0.03) to two-component butanol/acetone (10 g L)-1/10 g L-1) The column-penetrating adsorption curve of (a) shows: the breakthrough time increased as the butanol concentration decreased and the adsorbed amount decreased to 117.8 mg g-1(ii) a While the acetone adsorption amount increased to 50.9 mg g-1. This is because, after reducing the concentration of butanol, the competitive adsorption between the two is reduced, and the final butanol/acetone selectivity is 2.5.
Claims (7)
1. Zeolite imidazolate framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]The preparation method is characterized by comprising the following specific synthesis steps:
(1) mixing and stirring 87.5mL of N, N-dimethylformamide and 12.5mL of deionized water uniformly at room temperature to form a solution A, and dividing the solution A into two parts;
(2) the raw materials for synthesis are zinc nitrate hexahydrate, 2-methylimidazole and 5- (6) -methylbenzimidazole; dissolving 1.33g of zinc nitrate hexahydrate in one part of the solution A, and uniformly stirring to form a solution B; dissolving two imidazole ligands in the other solution A, and uniformly mixing to form a solution C;
(3) transferring the solution C into a reaction kettle, and then adding the solution B into the reaction kettle; reacting for 3-5 days at 100-120 ℃;
(4) waiting for the reaction kettle to coolThen, the obtained sample was washed several times with ethanol, filtered at room temperature, and dried to obtain a zeolitic imidazolate framework CHA- [ Zn (2-mIm)x(mbIm)2-x]。
2. The zeolitic imidazolate framework material CHA- [ Zn (2-mIm) of claim 1x(mbIm)2-x]The preparation method is characterized by comprising the following steps: in the step (2), the raw materials are in the following ratio: the synthesis molar ratio of the divalent metal Zn salt, 2-methylimidazole and 5(6) -methylbenzimidazole is controlled to be 1.0: 0.75-1.25: 1.25 or 1.0: 3.0-4.0: 1.25; namely, the molar ratio of the two imidazole ligands is 0.75-1.25: 1.25 or 3.0-4.0: 1.25.
3. the zeolitic imidazolate framework material CHA- [ Zn (2-mIm) of claim 2x(mbIm)2-x]The preparation method is characterized by comprising the following steps: when the molar ratio of the 2-methylimidazole to the 5(6) -methylbenzimidazole in the raw material ratio is 0.75-1.25: 1.25, CHA- [ Zn (2-mIm) described in step (4)x(mbIm)2-x]Has a chemical composition of x =0.70 ± 0.02; BET of 100. + -. 25m2(ii)/g; simultaneously measuring the cage diameter to be 5.5A; when the molar ratio of the 2-methylimidazole to the 5(6) -methylbenzimidazole in the raw material ratio is 3.0-4.0: 1.25, CHA- [ Zn (2-mIm) described in step (4)x(mbIm)2-x]Has a chemical composition of x =0.83 ± 0.03; BET of 600. + -. 25m2(ii)/g; the cage diameter was measured to be 8.1A.
4. A zeolitic imidazolate framework material CHA- [ Zn (2-mIm) prepared by the method of any one of claims 1 to 3x(mbIm)2-x]The application of butanol and acetone in adsorption separation of mixed water solution is provided.
5. Use according to claim 4, characterized in that: the adsorption separation performance test adopts static adsorption experiment or dynamic column adsorption experiment, in the static adsorption experiment, the concentration of butanol in the butanol and acetone mixed water solution is 0.2-20 g L-1The concentration of acetone is 0.2-20 g L-1(ii) a Dynamic column adsorptionIn the experiment, the concentration range of the butanol in the mixed aqueous solution of the butanol and the acetone is 10-20g L-1The concentration range of the acetone is 10-20g L-1。
6. Use according to claim 5, characterized in that: in the static adsorption experiment: CHA- [ Zn (2-mIm)x(mbIm)2-x]Activating for 36 h by using methanol at room temperature, preparing into particles with the particle size of 500-600 mu m, and then activating for 12 h in vacuum at 150 ℃; weighing 0.05-0.1 g of adsorbent particles, placing the adsorbent particles in a 5mL centrifuge tube, adding 5mL of butanol/acetone mixed solution with different concentrations, and standing for 24 h in an environment at 25 ℃ to ensure that adsorption saturation is achieved; finally, the sample is centrifuged, the supernatant is filtered through a membrane, and the concentration of the filtrate is analyzed by gas chromatography.
7. Use according to claim 5, characterized in that: in the dynamic column adsorption experiment: CHA- [ Zn (2-mIm)x(mbIm)2-x]Activating with methanol at room temperature for 36 h, preparing into 500-600 μm particles, and vacuum activating at 150 deg.C for 12 h; then, filling the adsorbent particles into a stainless steel packed column, wherein quartz wool is filled at two ends of the packed column, and the height of the packing is 25 cm; at the ambient temperature of 25 ℃, the butanol/acetone mixed solution is injected for 0.05 to 0.1 mL min by a high-pressure injection pump-1The flow rate of the mixed solution flows through the packing layer from bottom to top, a 2 mL chromatographic bottle is used for receiving effluent at the outlet end, a sample is collected every 10 min, and the concentration of the effluent is analyzed by gas chromatography.
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| CN114015063A (en) * | 2021-10-22 | 2022-02-08 | 太原理工大学 | Nitro-ligand-doped zeolitic imidazolate framework material ZIF-71-clnImxPreparation and use of |
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| CN114015063B (en) * | 2021-10-22 | 2023-01-10 | 太原理工大学 | Nitro-ligand-doped zeolitic imidazolate framework material ZIF-71-clnIm x Preparation and use of |
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