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 PDF

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CN113354829A
CN113354829A CN202110675399.3A CN202110675399A CN113354829A CN 113354829 A CN113354829 A CN 113354829A CN 202110675399 A CN202110675399 A CN 202110675399A CN 113354829 A CN113354829 A CN 113354829A
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石琪
孟倩倩
王江
董晋湘
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Taiyuan University of Technology
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Abstract

本发明公开了一种具有CHA拓扑结构的沸石咪唑酯骨架材料CHA‑[Zn(2‑mIm)x(mbIm)2‑x]的制备方法和应用。本发明通过改变两种配体投料摩尔比合成了具有不同化学组成，BET比表面积和笼径的CHA‑[Zn(2‑mIm)x(5‑mbIm)2‑x]（x=0.70±0.02和x=0.83±0.03）材料。本发明提供的CHA‑[Zn(2‑mIm)x(5‑mbIm)2‑x]（x=0.70±0.02）优先吸附分子链短的丙酮，能够实现丙酮丁醇的位阻分离；CHA‑[Zn(2‑mIm)x(5‑mbIm)2‑x]（x=0.83±0.03）优先吸附丁醇，能够实现丁醇丙酮的热力学分离。

Figure 202110675399

The invention discloses a preparation method and application of a zeolite imidazolate framework material CHA-[Zn(2-mIm) x (mbIm) 2-x ] with a CHA topology. The present invention synthesizes CHA-[Zn(2-mIm) x (5-mbIm) 2-x ] (x=0.70±0.02 with different chemical compositions, BET specific surface area and cage diameter by changing the molar ratio of two kinds of ligands) and x = 0.83 ± 0.03) Materials. CHA-[Zn(2-mIm) x (5-mbIm) 2-x ] (x=0.70±0.02) provided by the invention preferentially adsorbs acetone with short molecular chains, and can realize the steric separation of acetone butanol; CHA- [Zn(2‑mIm) x (5‑mbIm) 2‑x ] (x=0.83±0.03) preferentially adsorbs butanol, enabling the thermodynamic separation of butanol and acetone.

Figure 202110675399

Description

Zeolite imidazolate framework material CHA- [ Zn (2-mIm)x(mbIm)2-x]Preparation and use of
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.沸石咪唑酯骨架材料CHA-[Zn(2-mIm)x(mbIm)2-x]的制备方法，其特征在于具体合成步骤如下：1. the preparation method of zeolite imidazolate framework material CHA-[Zn(2-mIm) x (mbIm) 2-x ], is characterized in that concrete synthesis step is as follows: （1）室温下将87.5mL的N,N-二甲基甲酰胺和12.5mL的去离子水混合搅拌均匀形成溶液A并均分为两份；(1) At room temperature, 87.5 mL of N,N-dimethylformamide and 12.5 mL of deionized water were mixed and stirred to form solution A and divided into two equal parts; （2）合成原料使用六水硝酸锌，2-甲基咪唑和5(6)-甲基苯并咪唑；将1.33g六水硝酸锌溶于其中一份溶液A中，搅拌均匀形成溶液B；将两种咪唑配体溶于另一份溶液A中，混合均匀形成溶液C；(2) Zinc nitrate hexahydrate, 2-methylimidazole and 5(6)-methylbenzimidazole are used as the synthetic raw materials; 1.33g of zinc nitrate hexahydrate is dissolved in one of the solutions A, and the solution B is formed by stirring uniformly; Dissolve two imidazole ligands in another part of solution A, and mix well to form solution C; （3）先将溶液C转移到反应釜中，随后再加入溶液B至反应釜中；在100-120 ℃下反应3-5天；(3) Transfer solution C to the reactor first, then add solution B to the reactor; react at 100-120 °C for 3-5 days; （4）待反应釜冷却后，将得到的样品用乙醇洗涤数次，室温过滤、干燥，制得沸石咪唑酯骨架材料CHA-[Zn(2-mIm)x(mbIm)2-x]。(4) After the reaction kettle was cooled, the obtained sample was washed several times with ethanol, filtered and dried at room temperature to obtain the zeolite imidazolate framework material CHA-[Zn(2-mIm) x (mbIm) 2-x ]. 2.根据权利要求1所述的沸石咪唑酯骨架材料CHA-[Zn(2-mIm)x(mbIm)2-x]的制备方法，其特征在于：步骤（2）中，原料的配比为：二价金属Zn盐、2-甲基咪唑和5(6)-甲基苯并咪唑的合成摩尔比控制为1.0：0.75~1.25：1.25或者1.0：3.0~4.0：1.25；即所述两种咪唑配体的摩尔比为0.75~1.25：1.25或者为3.0~4.0：1.25。2. the preparation method of zeolite imidazolate framework material CHA-[Zn(2-mIm) x (mbIm) 2-x ] according to claim 1, is characterized in that: in step (2), the proportioning of raw material is : The synthesis molar ratio of 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; The molar ratio of imidazole ligands is 0.75~1.25:1.25 or 3.0~4.0:1.25. 3.根据权利要求2所述的沸石咪唑酯骨架材料CHA-[Zn(2-mIm)x(mbIm)2-x]的制备方法，其特征在于：当原料配比中2-甲基咪唑与5(6)-甲基苯并咪唑的摩尔比为0.75~1.25：1.25时，步骤（4）所述的CHA-[Zn(2-mIm)x(mbIm)2-x]中的化学组成为x = 0.70±0.02；BET为100±25 m2/g；同时测得笼径为5.5 Å；当原料配比中2-甲基咪唑与5(6)-甲基苯并咪唑的摩尔比为3.0~4.0：1.25时，步骤（4）所述的CHA-[Zn(2-mIm)x(mbIm)2-x]的化学组成为x= 0.83±0.03；BET为600±25 m2/g；测得其笼径为8.1 Å。3. the preparation method of zeolite imidazolate framework material CHA-[Zn(2-mIm) x (mbIm) 2-x ] according to claim 2, is characterized in that: when 2-methylimidazole and When the molar ratio of 5(6)-methylbenzimidazole is 0.75~1.25:1.25, the chemical composition in the CHA-[Zn(2-mIm) x (mbIm) 2-x ] described in step (4) is: x = 0.70±0.02; BET is 100±25 m 2 /g; the cage diameter is measured to be 5.5 Å; when the molar ratio of 2-methylimidazole to 5(6)-methylbenzimidazole in the raw material ratio is From 3.0 to 4.0: 1.25, the chemical composition of CHA-[Zn(2-mIm) x (mbIm) 2-x ] described in step (4) is x= 0.83±0.03; BET is 600±25 m 2 /g ; its cage diameter was measured to be 8.1 Å. 4.一种权利要求1~3任一项所述的方法制备得到的沸石咪唑酯骨架材料CHA-[Zn(2-mIm)x(mbIm)2-x]在吸附分离混合水溶液中丁醇和丙酮的应用。4. the zeolite imidazolate framework material CHA-[Zn(2-mIm) x (mbIm) 2-x ] prepared by the method described in any one of claims 1 to 3 is in butanol and acetone in the adsorption separation mixed aqueous solution Applications. 5.根据权利要求4所述的应用，其特征在于：吸附分离性能测试选用静态吸附实验或动态柱吸附实验，静态吸附实验中，丁醇和丙酮混合水溶液中丁醇的浓度为0.2-20 g L-1，丙酮的浓度为0.2-20 g L-1；动态柱吸附实验中，丁醇和丙酮混合水溶液中丁醇的浓度范围为10-20g L-1，丙酮的浓度范围为10-20g L-1。5. application according to claim 4, it is characterized in that: the adsorption separation performance test selects static adsorption experiment or dynamic column adsorption experiment, in static adsorption experiment, the concentration of butanol in butanol and acetone mixed aqueous solution is 0.2-20 g L -1 , the concentration of acetone is 0.2-20 g L -1 ; in the dynamic column adsorption experiment, the concentration range of butanol in the mixed aqueous solution of butanol and acetone is 10-20 g L -1 , and the concentration range of acetone is 10-20 g L -1 1 . 6.根据权利要求5所述的应用，其特征在于：静态吸附实验中：将CHA-[Zn(2-mIm)x(mbIm)2-x]在室温下用甲醇活化36 h并制成500-600 μm的颗粒，然后在150 ºC下真空活化12 h；称取0.05-0.1 g吸附剂颗粒置于5 mL离心管中，加入5 mL不同浓度的丁醇/丙酮混合液，然后在25 ºC环境中静置24 h确保达到吸附饱和；最后将样品离心、取上清液过滤膜，通过气相色谱分析滤液浓度。6. application according to claim 5 is characterized in that: in static adsorption experiment: CHA-[Zn(2-mIm) x (mbIm) 2-x ] is activated with methanol at room temperature for 36 h and made 500 -600 μm particles, then vacuum activated at 150 ºC for 12 h; weigh 0.05-0.1 g of adsorbent particles into a 5 mL centrifuge tube, add 5 mL of butanol/acetone mixtures of different concentrations, and then store at 25 ºC Let stand for 24 h in the environment to ensure adsorption saturation; finally, centrifuge the sample, take the supernatant filter membrane, and analyze the filtrate concentration by gas chromatography. 7.根据权利要求5所述的应用，其特征在于：动态柱吸附实验中：将CHA-[Zn(2-mIm)x(mbIm)2-x]在室温下用甲醇活化36 h后将其制成500-600 μm的颗粒，在150 ℃下真空活化12 h；然后将吸附剂颗粒装入不锈钢填料柱中，填料柱两端用石英棉填充，填料高度为25cm；在25 ℃的环境温度下，通过高压注射泵将丁醇/丙酮混合液以0.05 -0.1 mL min-1的流速自下而上流过填料层，在出口端用2 mL的色谱小瓶接流出液，每隔10 min收集一个样品，并通过气相色谱分析流出液浓度。7. application according to claim 5 is characterized in that: in the dynamic column adsorption experiment: CHA-[Zn(2-mIm) x (mbIm) 2-x ] is activated with methanol at room temperature after 36 h by its Particles of 500-600 μm were prepared and activated in vacuum at 150 °C for 12 h; then the adsorbent particles were packed into stainless steel packing columns, and both ends of the packing column were filled with quartz wool, and the packing height was 25 cm; at an ambient temperature of 25 °C Then, the butanol/acetone mixture was flowed through the packing layer from bottom to top at a flow rate of 0.05-0.1 mL min -1 through a high-pressure syringe pump, and a 2 mL chromatographic vial was used to receive the effluent at the outlet end, and a chromatographic vial was collected every 10 min. samples, and analyze the effluent concentration by gas chromatography.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130197235A1 (en) * 2012-01-30 2013-08-01 Georgia Tech Research Corporation Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by a Mixed-Ligand Synthetic Approach
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
US20190282997A1 (en) * 2018-03-16 2019-09-19 Exxonmobil Research And Engineering Company Ligand-exchanged zeolite imidazolate frameworks
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130197235A1 (en) * 2012-01-30 2013-08-01 Georgia Tech Research Corporation Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by a Mixed-Ligand Synthetic Approach
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
US20190282997A1 (en) * 2018-03-16 2019-09-19 Exxonmobil Research And Engineering Company Ligand-exchanged zeolite imidazolate frameworks
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NGUYEN N T T等: "Selective capture of carbon dioxide under humid conditions byhydrophobic chabazite‐type zeolitic imidazolate frameworks", 《ANGEWANDTECHEMIE》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114015063B (en) * 2021-10-22 2023-01-10 太原理工大学 Preparation and application of zeolite imidazolate framework material ZIF-71-clnImx doped with nitro ligands

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