CN113354829B - Zeolitic imidazolate framework material CHA- [ Zn (2-mIm) x (mbIm) 2-x ]Preparation and use of - Google Patents
Zeolitic 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 structure x (mbIm) 2‑x ]The preparation method and the application thereof. The 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 ligands x (5‑mbIm) 2‑x ](x =0.70 ± 0.02 and x =0.83 ± 0.03) material. The CHA- [ Zn (2-mIm) provided by the invention x (5‑mbIm) 2‑x ](x =0.70 ± 0.02) preferentially adsorbs acetone with a short molecular chain, and can realize steric hindrance separation of acetone and butanol; CHA- [ Zn (2-mIm) x (5‑mbIm) 2‑x ](x =0.83 ± 0.03) preferentially adsorb butanol, enabling thermodynamic separation of butanol acetone.
Description
Technical Field
The invention relates to a zeolite imidazolate framework material CHA- [ Zn (2-mIm) with CHA topology x (mbIm) 2-x ]The preparation method and the application thereof in the aspect of adsorption separation. In particular to a method for regulating 2-methylimidazole (2-mIm) and 5 (6) -methylbenzimidazole (mIm) in CHA- [ Zn (2-mIm) x (mbIm) 2-x ]The cage diameter is changed according to the molar ratio in the process, so that the separation of butanol and acetone is realized. Belonging to the application field of inorganic functional materials.
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.
Studies have now been carried out on 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 synthesis of structures [ J.sub.J. ]]Angewandte Chemie, 2014, 126 (40): 10821-10824) and investigated its hydrophilicity and hydrophobicity and its resistance to CO 2 /N 2 The adsorption separation performance of (1). The synthesis method of ZIF-302 in the study is as follows: according to the following divalent metal Zn salt: 2-methylimidazole (2-mIm): 5 (6) -methylbenzimidazole (mbIm) = 1.0: 0.86: 1.0 as a raw material molar ratio, the raw materials are sequentially added to a mixed solvent of N, N-dimethylformamide and water (volume ratio 19: 1) at room temperature, and a reaction is carried out at 120 ℃ to obtain a product, and finally the BET of the ZIF-302 material is 240 m as measured by Ar 2 (iv) g. However, there is no report in the literature that CHA- [ Zn (2-mIm) can be changed by a method of controlling the molar ratio of 2-methylimidazole (2-mIm) to 5 (6) -methylbenzimidazole (mIm) ligands x (mbIm) 2-x ]BET and pore structure of the material. We therefore wanted to modify CHA- [ Zn (2-mIm) by adjusting the molar ratio of the two imidazole ligands mentioned above x (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 imidazolate framework material CHA- [ Zn (2-mIm) with a CHA topological structure x (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 imidazate framework material CHA- [ Zn (2-mIm) x (mbIm) 2-x ]Has an elliptical cage structure and has small molecule adsorbateStronger affinity. Since the butanol molecules are significantly larger in size than the acetone molecules, CHA- [ Zn (2-mIm) can be controlled 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 adjustment x (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 imidazate 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 (4.48mmol, 1.33g) in one portion of solution A, and stirring uniformly to form solution B;
respectively dissolving 2-methylimidazole (2-mIm) and 5 (6) -methylbenzimidazole (mIm) 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 to 1.25:1.25 or 3.0 to 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, washing the obtained sample by ethanol for a plurality of times, filtering and drying at room temperature to obtain the zeolite imidazolate framework material CHA- [ Zn (2-mIm) x (mbIm) 2-x ]。
(5) CHA- [ Zn (2-mIm) obtained by liquid nuclear magnetic analysis when the molar ratio of 2-methylimidazole (2-mIm) in the raw material mixture ratio is 0.75 to 1.25 x (mbIm) 2-x ]Has a chemical composition of x =0.70 ± 0.02; when the raw material ratio is middle, 2-methylimidazoleCHA- [ Zn (2-mIm) obtained by liquid nuclear magnetic analysis at a molar ratio of oxazole (2-mIm) of 3.0 to 4.0 x (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 method x (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 a butanol aqueous solution or an acetone aqueous solution is finally 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 -1 The 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 by methanol for 36 h at room temperature, then particles with the particle size of 500-600 mu m are prepared, and the material is activated by vacuum pumping at 150 ℃ for 12 h to remove guest molecules; weighing 0.05-0.1 g adsorbent particles, placing in 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 ]Activating the material with methanol at room temperature for 36 h, preparing into particles of 500-600 μm, and vacuum-activating at 150 deg.C for 12 h 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 the height of the packed layer was 25 cm. Respectively mixing butanol/acetone mixed solution with butanol/acetone mixed solution at 25 deg.C by high pressure injection pumpThe concentration of alcohol is in the range of 10-20g L -1 The concentration range of the acetone is 10-20g L -1 At a rate of 0.05-0.1 mL min -1 The flow rate of the mixed solution flows through the packing layer from bottom to top, then the effluent is connected with a 2 mL chromatographic bottle at the outlet end, a sample is collected every 10 min, and the concentration of the sample is quantitatively analyzed by gas chromatography.
The invention has the beneficial effects that:
(1) Compared with the reported ZIF-302 material, the CHA- [ Zn (2-mIm) provided by the invention 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 diameter x (5-mbIm) 2-x ](x =0.70 ± 0.02 or x =0.83 ± 0.03).
(2) The CHA- [ Zn (2-mIm) provided by the invention 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 1 x (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 2 x (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 2 x (mbIm) 2-x ](x =0.70 ± 0.02 and x =0.83 ± 0.03) CO at 273K 2 Adsorption Curve and CO 2 The aperture profile.
FIG. 4 shows CHA- [ Zn (2-mIm) in example 3 x (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 4 x (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 5 x (mbIm) 2-x ](x =0.83 ± 0.03) two-component dynamic column adsorption profile for 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: synthesized according to the raw material molar ratio of zinc nitrate hexahydrate (99.0%, national drug group chemical reagents limited) to 2-methylimidazole (98.0%, alatin reagent (shanghai) limited) to 5 (6) -methylbenzimidazole (98.0%, pee medicine technology limited) = 1.0: 1.75 to 1.25/3.0 to 4.0) to 1.25, as follows:
(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 (4.48mmol, 1.33g) in one portion of solution A, and stirring uniformly to form solution B; mixing 2-methylimidazole (2-mIm) and 5-methylbenzimidazole in a molar ratio of 0.75 to 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, washing the obtained sample by ethanol for a plurality of times, filtering and drying at room temperature to obtain the zeolite imidazolate framework material CHA- [ Zn (2-mIm) x (mbIm) 2-x ]。
(5) CHA- [ Zn (2-mIm) obtained by liquid nuclear magnetic analysis when the molar ratio of 2-methylimidazole (2-mIm) synthesized in the raw material ratio is 0.75 to 1.25 x (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 molar ratio of 2-methylimidazole (2-mIm) in the raw material mixture ratio is 3.0 to 4.0 x (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) compounds of different chemical compositions x (mbIm) 2-x ]The diffraction pattern of (a). By comparison, it was found that the 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, respectively x (mbIm) 2-x ]Ar adsorption desorption isotherm and CO of material 2 Adsorption isotherms. Calculating CHA- [ Zn (2-mIm) x (mbIm) 2-x ](x =0.70 ± 0.02 and x =0.83 ± 0.03) BET of 100 ± 25m, respectively 2 The sum of the amounts of the components is 600 +/-25 m 2 (iv) 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 1 x (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 hours by using methanol at room temperature, then prepared into particles of 500-600 mu m, and then is activated for 12 hours by vacuumizing at 150 ℃ to remove solvent molecules. 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: weighing 0.1 g adsorbent particles, placing in 10 mL centrifuge tube, adding 5mL butanol (0.2-20 g L) with different concentrations -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 show thatThe maximum adsorption amounts of acetone were 111.4 mg g -1 And 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 diameter x (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 diameter x (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 1 x (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 hours by methanol at room temperature, then particles with the particle size of 500-600 microns are prepared, then the vacuum activation is carried out for 12 hours at the temperature of 150 ℃ to remove solvent molecules, and then a pipeline is rinsed by a bi-component butanol/acetone mixed solution to ensure that the concentration of the solution 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 ℃, the bi-component butanol/acetone mixed solution is injected into the reactor for 0.05 mL min by a high-pressure injection pump -1 The flow rate of the mixed solution was passed through the packing layer from bottom to top, and the discharge liquid was connected to the outlet, and 0.5 mL of a sample was collected every 10 min with a 2 mL chromatography vial, and the concentration was analyzed 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 -1 Significantly greater than the dynamic adsorption capacity of butanol. The dynamic selectivity of acetone/butanol was calculated to be 3.2, since butaneAlcohol molecules are limited by the cage diameter of the material and can hardly enter the pore channel, and finally, the steric hindrance separation of acetone and butanol is realized. FIG. 5 (b) shows CHA- [ Zn (2-mIm) x (mbIm) 2-x ](x =0.70 ± 0.02) p-binary 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 (c): 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 amount of acetone adsorbed 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 1 x (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 hours by methanol at room temperature, then prepared into particles of 500-600 mu m, then vacuumized and activated for 12 hours 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 packed layer is 25 cm; at the environmental temperature of 25 ℃, the bi-component butanol/acetone mixed solution is injected into the reactor for 0.05 mL min by a high-pressure injection pump -1 The flow rate of the mixed solution flows through the packing layer from bottom to top, the outlet end is connected with the discharge liquid, a 2 mL chromatographic vial is used for collecting 0.5 mL samples every 10 min, and then the concentration of the samples is quantitatively analyzed in turn through gas chromatography.
FIG. 6 (a) shows the adsorbent versus two components 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 amount of acetone in the final balance is 34.2 mg g -1 At this time, the dynamic selectivity of butanol/acetone is 2.0, and the effect of acetone/butanol can be achievedAnd (4) performing thermodynamic separation.
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, when the concentration of butanol is reduced, competitive adsorption between the two is reduced, and the final butanol/acetone selectivity is 2.5.
Claims (5)
1. Zeolite imidazate framework material CHA- [ Zn (2-mIm) x (mbIm) 2-x ]The application of butanol and acetone in adsorption separation of mixed aqueous solution is characterized in that:
the zeolite imidazolate 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 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) After the reaction kettle is cooled, washing the obtained sample for a plurality of times by using ethanol, filtering and drying at room temperature to obtain the zeolite imidazole ester framework material CHA- [ Zn (2-mIm) x (mbIm) 2-x ]；
In the step (2), the mixture ratio of the raw materials is as follows: the synthesis molar ratio of the divalent metal Zn salt, 2-methylimidazole and 5 (6) -methylbenzimidazole is controlled to be 1.0:0.75 to 1.25:1.25 or 1.0:3.0 to 4.0:1.25; namely, the molar ratio of the two imidazole ligands is 0.75 to 1.25:1.25 or 3.0 to 4.0:1.25.
2. use according to claim 1, characterized in that: when the molar ratio of the 2-methylimidazole to the 5 (6) -methylbenzimidazole in the raw material ratio is 0.75 to 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. + -. 25m 2 (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 to 4.0:1.25 hours, 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. + -. 25m 2 (ii)/g; the cage diameter was measured to be 8.1A.
3. Use according to claim 1, characterized in that: the adsorption separation performance test adopts static adsorption experiment or dynamic column adsorption experiment, wherein in the static adsorption experiment, the concentration of butanol in the mixed water solution of butanol and acetone is 0.2-20 g L -1 The concentration of acetone is 0.2-20 g L -1 (ii) a In dynamic column adsorption experiment, the concentration range of butanol in the mixed water solution of butanol and acetone is 10-20g L -1 The concentration range of the acetone is 10-20g L -1 。
4. Use according to claim 3, characterized in that: in the static adsorption experiment: CHA- [ Zn (2-mIm) x (mbIm) 2-x ]Activating with methanol at room temperature for 36 h, preparing into particles of 500-600 μm, and vacuum activating at 150 deg.C for 12 h; weighing 0.05-0.1 g of adsorbent particles, placing the adsorbent particles in a 5mL centrifugal tube, adding 5mL of butanol/acetone mixed solution with different concentrations, and then 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.
5. Use according to claim 4, 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, making into 500-600 μm granule, and vacuum activating at 150 deg.C for 12 h; then the adsorbent particles are packedPutting the mixture into a stainless steel filler column, wherein two ends of the filler column are filled with quartz wool, and the height of the filler 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 -1 The flow rate of the mixed solution flows through the packing layer from bottom to top, the effluent is connected with a 2 mL chromatographic bottle at the outlet end, one sample is collected every 10 min, and the concentration of the effluent is analyzed through gas chromatography.
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| CN103951684A (en) * | 2014-04-10 | 2014-07-30 | 吉林大学 | Mixed ligand zeolitic imidazole framework, preparation method and application to carbon dioxide selective adsorption |
| CN110483787A (en) * | 2019-03-12 | 2019-11-22 | 中国石油大学(北京) | A kind of zeolitic imidazolate framework material and preparation method thereof |
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| WO2019177771A1 (en) * | 2018-03-16 | 2019-09-19 | Exxonmobil Research And Engineering Company | Ligand-exchanged zeolitic imidazolate frameworks |
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| CN103951684A (en) * | 2014-04-10 | 2014-07-30 | 吉林大学 | Mixed ligand zeolitic imidazole framework, preparation method and application to carbon dioxide selective adsorption |
| CN110483787A (en) * | 2019-03-12 | 2019-11-22 | 中国石油大学(北京) | A kind of zeolitic imidazolate framework material and preparation method thereof |
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| Selective capture of carbon dioxide under humid conditions byhydrophobic chabazite‐type zeolitic imidazolate frameworks;Nguyen N T T等;《AngewandteChemie》;20140717;第126卷(第40期);10821-10824 * |
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