Application of a hetero[3]aromatic crystalline material in the adsorption and separation of pyrrolidine and tetrahydrofuran mixtures and / or the capture of iodine vapor

Abstract

This invention discloses the application of a hetero[3]aromatic crystalline material in the adsorption and separation of a mixture of pyrrolidine and tetrahydrofuran and / or the capture of iodine vapor. It relates to the field of adsorption technology. Firstly, a novel hetero[3]aromatic crystalline material capable of adsorbing and separating pyrrolidine and tetrahydrofuran to achieve iodine capture is synthesized. The application method includes: selectively adsorbing pyrrolidine in a mixture of pyrrolidine and tetrahydrofuran using the novel hetero[3]aromatic crystalline material to obtain a pyrrolidine-hetero[3]aromatic crystalline material, achieving the separation of tetrahydrofuran and pyrrolidine, and capturing iodine vapor using the pyrrolidine-hetero[3]aromatic crystalline material. Compared with other macrocyclic aromatics, this invention not only achieves the separation of tetrahydrofuran and pyrrolidine, but also has advantages such as high iodine adsorption capacity and good thermal stability; at the same time, the synthesis method has advantages such as simple operation, high yield, simple post-processing, and easy separation and purification of the product.

Description

Technical Field

[0001] This invention relates to the field of adsorption technology, and more specifically, to the application of a novel hetero[3]aromatic crystalline material in the adsorption and separation of a mixture of pyrrolidine and tetrahydrofuran and / or the capture of iodine vapor. Background Technology

[0002] With the development of supramolecular chemistry, the design and synthesis of supramolecular macrocyclic hosts with tunable cavity structures and specific recognition capabilities has always been an important research direction in this field. While traditional macrocyclic molecules such as crown ethers, cyclodextrins, and calixarnes have been extensively studied, their structural uniformity and functional limitations restrict their application in complex separation systems and molecular recognition. In recent years, the strategy of integrating building blocks of different structures into the same macrocyclic framework has provided new ideas for developing novel hybrid macrocyclic hosts and overcoming their performance bottlenecks. These hybrid macrocycles can not only achieve selective recognition through precise control of cavity size and shape, but also introduce multiple binding sites, significantly improving their binding capacity and separation efficiency for specific guests. In the field of adsorption separation, hybrid macrocyclic molecules exhibit unique advantages. For example, the biphenyl-derived macrocyclic compounds developed by Stoddart's group achieved highly efficient and selective adsorption of heavy metal ions in water through π-π stacking and electrostatic synergy; in addition, the triazine heterocyclic macrocyclic molecules designed by Yang's team, with their rigid cavities and multiple hydrogen bonding sites, have been successfully used for the rapid separation and enrichment of organic pollutants. These studies demonstrate that by rationally designing the structure of hybrid macrocycles, their host-guest interaction modes can be modulated, thereby achieving highly selective capture and separation of specific targets. While breakthroughs have been made in the research of integrated functional materials such as "adsorption-catalysis" and "separation-detection" in recent years, three-functional integrated materials combining "selective separation-structure-activity conversion-iodine adsorption" remain undeveloped. The core challenge lies in designing a synergistic mechanism of "recognition site-structure-activity linkage-iodine adsorption site," ensuring both high separation selectivity and stable iodine adsorption activity in the new structure formed after adsorbing organic matter.

[0003] Because pyrrolidine and tetrahydrofuran have similar boiling points, distillation and rectification processes consume a significant amount of energy. Furthermore, porous materials have relatively weak chemical stability, and their structure is highly susceptible to destruction in high temperatures, acidic or alkaline environments, and even aqueous phases. Additionally, most iodine capture technologies rely on single physical adsorption or chemical reactions, lacking a synergistic "adsorption-fixation" mechanism. While porous materials, such as metal-organic frameworks and covalent organic frameworks, have high adsorption capacities, they suffer from poor thermal stability; high temperatures can lead to bond breakage and framework structure collapse. Moreover, traditional macrocyclic materials have low adsorption capacities (mostly below 2 g·g⁻¹). -1Furthermore, its ability to stabilize iodine is insufficient, making long-term fixation difficult. Chinese Patent Publication No. CN120463956A discloses a benzimidazole-based deep-cavitary calixarene crosslinked polymer, its preparation method, and its application in iodine adsorption. An insoluble benzimidazole-based deep-cavitary calixarene crosslinked polymer, NCCP-I, is prepared using a simple synthetic route. NCCP-I is non-porous, with an irregular crystal structure and amorphous dense particles, and it possesses high thermal stability. The saturated adsorption capacity of NCCP-I for iodine vapor is only 1.36 g·g⁻¹. -1 This cannot meet the application requirements and lacks competitiveness. Chinese patent with publication number CN117534547A discloses a hetero[3]aromatic macrocyclic compound and its preparation method and application. The hetero[3]aromatic macrocyclic compound is formed by integrating ethoxybiphenyl and methoxyphenol on a ring skeleton and introducing hydroxyl functional groups into the structure, thereby having the ability to effectively capture iodine. According to the test in Example 1, the hetero[3]aromatic macrocyclic compound adsorbed iodine at a rate of 2 g / g (66 wt%) for 30 min, which also showed the defect of low adsorption capacity. Summary of the Invention

[0004] This invention addresses the shortcomings of existing technologies for separating pyrrolidine and tetrahydrofuran, such as high energy consumption, cumbersome processes, and the need for high-purity desorbents, as well as the aforementioned shortcomings of iodine capture technology, such as poor thermal stability, low adsorption capacity, and insufficient iodine stability. It provides a novel hetero[3]aromatic crystalline material for the adsorption and separation of pyrrolidine and tetrahydrofuran mixtures and / or the capture of iodine vapor. Firstly, a novel hetero[3]aromatic crystalline material capable of adsorbing and separating pyrrolidine and tetrahydrofuran to achieve iodine capture is synthesized. Compared to other macrocyclic aromatics, this invention not only achieves the separation of tetrahydrofuran and pyrrolidine but also has advantages such as high iodine adsorption capacity and good thermal stability. Furthermore, compared to other hybrid macrocyclic synthesis methods, the novel hetero[3]aromatic synthesis method has advantages such as simple operation, high yield, simple post-processing, and easy product separation and purification.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] The application of a novel hetero[3]aromatic crystalline material in the adsorption and separation of a mixture of pyrrolidine and tetrahydrofuran and / or the capture of iodine vapor, wherein the preparation method of the novel hetero[3]aromatic crystalline material includes the following steps: dissolving 4,4′-bis(2-bromoethoxy)-1,1′-biphenyl, 1,3,5-trimethoxybenzene and paraformaldehyde in chloroform, adding trifluoroacetic acid to catalyze the reaction while stirring at room temperature, then heating and stirring, and after the reaction is complete and cooled to room temperature, adding saturated sodium carbonate solution to quench the reaction, separating the liquid by column chromatography to obtain crystals, and activating the crystals to obtain the novel hetero[3]aromatic crystalline material;

[0007] ;

[0008] The method of application includes: selectively adsorbing pyrrolidine in a mixture of pyrrolidine and tetrahydrofuran using the novel hetero[3]aromatic crystal material to obtain pyrrolidine-hetero[3]aromatic crystal material, thereby achieving the separation of tetrahydrofuran and pyrrolidine, and using the pyrrolidine-hetero[3]aromatic crystal material to capture iodine vapor.

[0009] Optionally, the molar ratio of 4,4′-bis(2-bromoethoxy)-1,1′-biphenyl, 1,3,5-trimethoxybenzene and paraformaldehyde is 1:2:3.

[0010] Optionally, the heating and stirring temperature is 65°C.

[0011] Optionally, the activation temperature is 150°C; the activation time is 12 hours.

[0012] Optionally, the mixture of pyrrolidine and tetrahydrofuran is a mixed vapor of pyrrolidine and tetrahydrofuran.

[0013] Optionally, the temperature for selective adsorption of pyrrolidine is 25°C.

[0014] Optionally, the volume ratio of pyrrolidine to tetrahydrofuran in the mixture of pyrrolidine and tetrahydrofuran is 1:1.

[0015] Optionally, the temperature for capturing iodine vapor is 80°C.

[0016] Optionally, the application method further includes: after selective adsorption of pyrrolidine, removing the mixture of pyrrolidine and tetrahydrofuran on the surface of the pyrrolidine-hetero[3]aromatic crystal material by vacuum heating, wherein the vacuum heating temperature is 45°C and the vacuum heating time is 30 min.

[0017] This invention utilizes novel hetero[3]aromatic macrocyclic molecules as solid adsorbents for the first time, achieving efficient and highly selective separation of pyrrolidine from a mixed vapor of pyrrolidine and tetrahydrofuran, with the obtained pyrrolidine purity reaching 98.9%. Particularly noteworthy is that the pyrrolidine-hetero[3]aromatic crystal material formed after capturing pyrrolidine can be further used for iodine capture, exhibiting not only excellent iodine adsorption capacity significantly higher than most porous organic materials and traditional adsorbents, but also superior thermal stability. This "one material, multiple uses, stepwise adsorption" strategy achieves synergistic processing from volatile organic compound separation to iodine capture, providing a novel integrated solution for the adsorption and resource recovery of complex systems.

[0018] Implementing the embodiments of the present invention will have the following beneficial effects:

[0019] (1) Synthesis and process: The synthetic route of the novel hetero[3]aromatic macrocyclic compound synthesized by this invention is simple, the reaction conditions are mild, the product is easy to separate and purify, and it has good reproducibility and scale-up potential; the process of adsorption separation of the mixture of pyrrolidine and tetrahydrofuran is simple to operate, without the need for complex equipment or high energy consumption steps, and is suitable for practical application.

[0020] (2) Outstanding adsorption performance: The novel hetero[3]aromatic macrocyclic compounds synthesized in this invention exhibit high adsorption capacity and high selectivity for pyrrolidine, and can achieve high-purity separation of pyrrolidine; more importantly, the crystal material formed after adsorbing pyrrolidine can be further used as iodine capture, and its iodine adsorption capacity is significantly higher than that of most porous organic materials, metal-organic frameworks and activated carbon and other traditional adsorbents. Attached Figure Description

[0021] Figure 1 The image shows a single crystal of the novel hetero[3]aromatic crystalline material of the present invention after adsorption of pyrrolidine.

[0022] Figure 2 The above is the 1H NMR spectrum of the novel hetero[3]aromatic crystalline material of Example 1 of this invention.

[0023] Figure 3 The image shows the carbon NMR spectrum of the novel hetero[3]aromatic crystalline material of Example 1 of this invention.

[0024] Figure 4 The image shows the nuclear magnetic mass spectrum of the novel hetero[3]aromatic crystalline material of Example 1 of this invention.

[0025] Figure 5 This is the single crystal structure of the novel hetero[3]aromatic crystalline material of Example 1 of the present invention.

[0026] Figure 6 The PXRD data of the novel hetero[3]aromatic crystalline material of Example 1 of the present invention and its adsorption of iodine vapor by pyrrolidine, tetrahydrofuran, pyrrolidine and tetrahydrofuran mixed vapor (v:v=1:1), and the pyrrolidine-hetero[3]aromatic crystalline material after adsorption of pyrrolidine.

[0027] Figure 7 The H-Pye NMR spectrum after adsorption of pyrrolidine in Example 2 of this invention is shown.

[0028] Figure 8 The image shows the 1H NMR spectrum of H-THF after adsorption of tetrahydrofuran in Example 2 of this invention.

[0029] Figure 9 Example 3 of this invention describes the adsorption of pyrrolidine and tetrahydrofuran at a ratio of 1:1. v : v The hydrogen NMR spectrum of H-Pye / THF after mixing vapor.

[0030] Figure 10 The headspace gas chromatography of the novel hetero[3]aromatic crystalline material of Example 1 of the present invention after adsorption of mixed vapors of pyrrolidine and tetrahydrofuran.

[0031] Figure 11 The time dependence curve of iodine vapor adsorption on the hetero[3]aromatic crystalline material after adsorption of pyrrolidine in Example 4 of the present invention is shown.

[0032] Figure 12 The time-dependent curve of iodine desorption of the hetero[3]aromatic crystalline material after adsorption of pyrrolidine in Example 5 of the present invention is shown. Detailed Implementation

[0033] The present invention will be further described below with reference to specific embodiments, but this does not limit the present invention in any way.

[0034] This invention discloses the application of a novel hetero[3]aromatic crystalline material in the adsorption and separation of a mixture of pyrrolidine and tetrahydrofuran and / or the capture of iodine vapor. The preparation method of the novel hetero[3]aromatic crystalline material includes the following steps: 4,4′-bis(2-bromoethoxy)-1,1′-biphenyl, 1,3,5-trimethoxybenzene and paraformaldehyde are dissolved in chloroform. Trifluoroacetic acid is added to catalyze the reaction while stirring at room temperature. Then, the mixture is heated and stirred. After the reaction is complete and cooled to room temperature, saturated sodium carbonate solution is added to quench the reaction. After separation by column chromatography, crystals are obtained. The crystals are then activated to obtain the novel hetero[3]aromatic crystalline material.

[0035] ;

[0036] The application methods include: selectively adsorbing pyrrolidine in a mixture of pyrrolidine and tetrahydrofuran using a novel hetero[3]aromatic crystalline material to obtain pyrrolidine-hetero[3]aromatic crystalline material, thereby achieving the separation of tetrahydrofuran and pyrrolidine, and using pyrrolidine-hetero[3]aromatic crystalline material to capture iodine vapor.

[0037] In one specific embodiment, the method used includes: placing a novel hetero[3]aromatic crystalline material in a mixture of pyrrolidine and tetrahydrofuran to selectively adsorb pyrrolidine, wherein the temperature for selective adsorption of pyrrolidine is 25°C.

[0038] Specifically, during the adsorption process, the novel hetero[3]aromatic crystal material undergoes a crystal form change. It achieves the separation of tetrahydrofuran and pyrrolidine based on the synergistic mechanism of "chemical reaction-host-guest interaction". Moreover, the host molecule of the novel hetero[3]aromatic crystal material can load four pyrrolidine guest molecules. The single crystal diagram of the novel hetero[3]aromatic crystal material after adsorbing pyrrolidine is shown in the figure. Figure 1As shown; the resulting pyrrolidine-hetero[3]aromatic crystalline material exhibits excellent iodine capture ability (5.63 g·g). -1 And thermal stability in a vacuum up to 150°C.

[0039] In one specific embodiment, the selective adsorption time can be varied by factors such as the amount of sample and the proportion of pyrrolidine in the mixture.

[0040] In one specific embodiment, the time for capturing iodine vapor can be varied depending on factors such as the amount of sample.

[0041] In one specific embodiment, the molar ratio of 4,4′-bis(2-bromoethoxy)-1,1′-biphenyl, 1,3,5-trimethoxybenzene and paraformaldehyde is 1:2:3.

[0042] In one specific embodiment, the heating and stirring temperature is 65°C.

[0043] In one specific embodiment, the activation temperature is 150°C and the activation time is 12 hours.

[0044] In one specific embodiment, the mixture of pyrrolidine and tetrahydrofuran is a mixed vapor of pyrrolidine and tetrahydrofuran.

[0045] In one specific embodiment, the volume ratio of pyrrolidine to tetrahydrofuran in the mixture of pyrrolidine and tetrahydrofuran is 1:1.

[0046] In one specific embodiment, the temperature at which iodine vapor is captured is 80°C.

[0047] In one specific embodiment, the application method further includes: after selective adsorption of pyrrolidine, removing the mixture of pyrrolidine and tetrahydrofuran on the surface of the pyrrolidine-hetero[3]aromatic crystal material by vacuum heating, the vacuum heating temperature is 45°C and the vacuum heating time is 30 min, and then capturing iodine vapor with the vacuum-heated pyrrolidine-hetero[3]aromatic crystal material.

[0048] Specifically, after the novel hetero[3]aromatic crystalline material is completely adsorbed in a mixture of pyrrolidine and tetrahydrofuran, it is removed and then the mixture of pyrrolidine and tetrahydrofuran adsorbed on the surface of the obtained pyrrolidine-hetero[3]aromatic crystalline material is removed by vacuum heating. The host-guest complex pyrrolidine-hetero[3]aromatic crystalline material formed at 45°C remains stable.

[0049] The following are specific embodiments.

[0050] Example 1

[0051] The preparation method of the novel hetero[3]aromatic crystalline material in this embodiment is as follows:

[0052] 4,4′-bis(2-bromoethoxy)-1,1′-biphenyl, 1,3,5-trimethoxybenzene and paraformaldehyde in a molar ratio of 1:2:3 were dissolved in chloroform. Trifluoroacetic acid was added to catalyze the reaction while stirring at room temperature. The mixture was then heated to 65°C and stirred. After the reaction was complete and cooled to room temperature, a saturated sodium carbonate solution was added to quench the reaction. The mixture was separated by column chromatography to obtain crystals. The obtained crystals were activated under vacuum at 150°C for 12 h to obtain a new white powder hetero[3]aromatic crystalline material, denoted as H. The reaction equation is shown below:

[0053] ;

[0054] The characterization data of the product prepared in this embodiment are as follows:

[0055] H, 1 H NMR (400 MHz, chloroform-d, 293 K) (ppm) : δ 7.19 (d, J = 8 Hz, 2H), 6.72 (d, J = 8 Hz, 2H), 6.34 (s, 2H), 6.29 (s, 2H), 4.39–4.29 (m, 4H), 4.22 (s, 1H), 4.18 (s, 1H), 4.12 (s, 2H), 3.91 (s, 6H), 3.72–3.65 (m, 16H), 3.53 (s, 1H), 3.49 (s, 1H). 13 C10 NMR (400 MHz, dichloromethane-d2, 293 K) δ(ppm): 159.60, 157.63, 157.84, 156.59, 155.06, 129.50, 133.44, 130.31, 127.55, 123.10, 116.43, 112.21, 111.13, 91.33, 68.37, 61.07, 55.54, 55.47, 29.91, 22.62, 16.31. High-resolution mass spectrometry value m / z: 793.0984, corresponding to ([C10] δ(ppm) ... 37 H 40 Br2O8]+Na) + Melting range: 330-332 ℃.

[0056] PXRD test results are as follows Figure 6 As shown, the obtained novel hetero[3]aromatic crystalline material has good crystallinity.

[0057] Example 2

[0058] The adsorption of pyrrolidine and tetrahydrofuran by the novel hetero[3]aromatic crystal material prepared in Example 1: Take two 20 mL inoculum bottles and add 1 mL of pyrrolidine and 1 mL of tetrahydrofuran respectively, named H-Pye and H-THF; Take 20 mg of the novel hetero[3]aromatic crystal material prepared in Example 1 and place it in two 5 mL open inoculum bottles respectively. Place the two open 5 mL inoculum bottles in the two 20 mL inoculum bottles respectively. Seal the 20 mL inoculum bottles and place them in a 25 ℃ water bath for 72 h. Place the obtained powder in a 45 ℃ vacuum oven for 30 min.

[0059] The characterization data of the product prepared in this embodiment are as follows:

[0060] H-Pye, 1 H NMR (400 MHz, CDCl3, 293 K) (ppm): δ 7.19 (d, J = 8 Hz, 2H), 6.75 (d, J = 8 Hz, 2H), 6.37 (s, 2H), 6.30 (s, 2H), 4.28–4.26 (m, 4H), 4.17(s, 1H), 4.13 (s, 1H), 4.11 (s, 2H), 3.90 (s, 6H), 3.70 (s, 6H), 3.64 (s, 6H), 3.48 (s, 1H), 3.44 (s, 1H), 4.28–4.26 (m, 9H), 3.15–3.12 (m, 4H), 2.91 (s, 8H), 2.04–2.00 (m, 9H), 1.91 (s, 8H).

[0061] H-THF, 1 H NMR (400 MHz, CDCl3, 293 K) (ppm): δ 7.19 (d, J = 8 Hz, 2H), 6.72 (d, J= 8 Hz, 2H), 6.39 (s, 2H), 6.30 (s, 2H), 4.39–4.27 (m, 4H), 4.22 (s,1H), 4.18 (s, 1H), 4.12 (s, 2H), 3.91 (s, 6H), 3.72–3.65 (m, 16H), 3.53 (s,1H), 3.49 (s, 1H).

[0062] 1 1H NMR results show that the novel hetero[3]aromatic crystal material has a significant adsorption effect on pyrrolidine, but no adsorption on tetrahydrofuran.

[0063] PXRD test results are as follows Figure 6 As shown, compared with the PXRD spectrum of the novel hetero[3]aromatic crystal material initially activated, the PXRD spectrum of the novel hetero[3]aromatic crystal material placed in pyrrolidine vapor for a period of time changed, indicating that its unit cell parameters had changed, indicating that the novel hetero[3]aromatic crystal material adsorbed pyrrolidine; the spectrum of the novel hetero[3]aromatic crystal material placed in tetrahydrofuran vapor for a period of time changed very little, indicating that its unit cell parameters hardly changed, meaning that the novel hetero[3]aromatic crystal material has no adsorption capacity for tetrahydrofuran.

[0064] Example 3

[0065] The novel hetero[3]aromatic crystalline material pyrrolidine and tetrahydrofuran prepared in Example 1 were mixed in a 1:1 ratio. v : v Adsorption of mixed vapor: Take a 20 mL culture bottle, add 1 mL pyrrolidine and 1 mL tetrahydrofuran, named H-Pye / THF, take 20 mg of the novel hetero[3] aromatic crystalline material prepared in Example 1 and place it in a 5 mL open culture bottle, place the open 5 mL culture bottle in the above 20 mL culture bottle, seal the 20 mL culture bottle, place it in a 25 ℃ water bath for 168 h, and place the obtained powder in a 45 ℃ vacuum oven for 30 min.

[0066] The characterization data of the product prepared in this embodiment are as follows:

[0067] H-Pye / THF, 1 H NMR (400 MHz, CDCl3, 293 K) (ppm): δ 7.19 (d, J = 8 Hz, 2H), 6.74 (d, J= 8 Hz, 2H), 6.36 (s, 2H), 6.29 (s, 2H), 4.22–4.11 (m, 8H), 3.90 (s, 6H), 3.70 (s, 6H), 3.63 (s, 6H), 3.48 (s, 1H), 3.44 (s, 1H), 4.31–4.28 (m, 8H), 3.07–3.04 (m, 4H), 2.79 (s, 7H), 2.02–1.99 (m, 8H), 1.86 (s, 7H).

[0068] exist 1 The H NMR spectrum only showed the signal of hydrogen atoms corresponding to pyrrolidine, which indicates that the novel hetero[3]aromatic crystal material can selectively adsorb pyrrolidine.

[0069] PXRD test results are as follows Figure 6 As shown, compared with the PXRD spectrum of the novel hetero[3]aromatic crystal material initially activated, the PXRD spectrum of the novel hetero[3]aromatic crystal material placed in a mixed vapor of pyrrolidine and tetrahydrofuran for a period of time changed, and the spectrum change was the same as that of H-Pye. This indicates that the novel hetero[3]aromatic crystal material can selectively adsorb pyrrolidine.

[0070] The results of headspace gas chromatography are as follows Figure 10 As shown, the results indicate that the novel hetero[3]aromatic crystalline material can selectively adsorb pyrrolidine with a selectivity of 98.9%.

[0071] Example 4

[0072] Adsorption of iodine vapor by crystalline material after adsorption of pyrrolidine: Take a 20 mL culture bottle and add 0.5-1.0 g of iodine. Take 20 mg of the novel hetero[3]aromatic crystalline material H-Pye after adsorption of pyrrolidine in Example 3. Place it in a 5 mL open culture bottle, place the open 5 mL culture bottle in the above 20 mL culture bottle, seal the 20 mL culture bottle, name it I2@H-Pye, place it in an 80 ℃ oven, take it out every 1 h to weigh it and calculate the amount of iodine adsorbed.

[0073] The time-dependent curve of H-Pye adsorption of iodine in Example 4 is as follows: Figure 11 The structure indicates that H-Pye has an extremely high iodine capture capacity (5.63 g·g). -1 ).

[0074] PXRD test results are as follows Figure 6As shown, compared with the PXRD spectrum of the novel hetero[3]aromatic crystalline material adsorbed with pyrrolidine, the PXRD spectrum of I2@H-Pye after adsorbing iodine vapor changed. H-Pye showed a typical crystal structure, while all the crystallization peaks of the sample (I2@H-Pye) disappeared after iodine adsorption saturation, indicating that the structure changed from the original crystalline state to the amorphous state.

[0075] Example 5

[0076] Thermal stability analysis of I2@H-Pye: 20 mg of material I2@H-Pye after adsorbing iodine vapor in Example 4 was placed in a vacuum oven at 150°C. It was taken out and weighed every 30 min, and the amount of iodine desorption was calculated.

[0077] The time-dependent curve of iodine desorption by I2@H-Pye in Example 5 is as follows: Figure 12 The results showed that I2@H-Pye has extremely high thermal stability, and can still maintain 98% iodine adsorption efficiency even under vacuum at a high temperature of 150 °C.

[0078] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. Use of a hetero[3]arene crystal material for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or the capture of iodine vapour, characterised in that, The preparation method of the hetero[3]arene crystal material comprises the following steps: 4,4'-di(2-bromoethoxy)-1,1'-biphenyl, 1,3,5-trimethoxybenzene and paraformaldehyde are dissolved in chloroform, and trifluoroacetic acid is added for catalytic reaction during stirring at room temperature, and then heating and stirring are performed, after the reaction is completed and cooled to room temperature, saturated sodium carbonate solution is added to quench the reaction, and after separation, column chromatography is performed to separate the crystals, and the crystals are activated to obtain the hetero[3]arene crystal material; ； The application method comprises: The hetero[3]arene crystal material is used for selectively adsorbing pyrrolidine in a mixture of pyrrolidine and tetrahydrofuran to obtain a pyrrolidine-hetero[3]arene crystal material, so as to separate tetrahydrofuran and pyrrolidine, and the pyrrolidine-hetero[3]arene crystal material is used for capturing iodine vapor.

2. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that The molar ratio of the 4,4'-di(2-bromoethoxy)-1,1'-biphenyl, 1,3,5-trimethoxybenzene and paraformaldehyde is 1:2:

3.

3. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that, The temperature of the heating and stirring is 65°C.

4. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that, The temperature of the activation is 150°C; and the time of the activation is 12h.

5. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that, The mixture of pyrrolidine and tetrahydrofuran is a mixed vapor of pyrrolidine and tetrahydrofuran.

6. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that, The temperature of the selective adsorption of pyrrolidine is 25°C.

7. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that The volume ratio of pyrrolidine and tetrahydrofuran in the mixture of pyrrolidine and tetrahydrofuran is 1:

1.

8. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that, The temperature of the capturing of iodine vapor is 80°C.

9. Use of the hetero[3]arene crystal material according to claim 1 for the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran and / or for the capture of iodine vapour, characterized in that, The application method further comprises: after the selective adsorption of pyrrolidine is completed, vacuum heating is performed to remove the mixture of pyrrolidine and tetrahydrofuran on the surface of the pyrrolidine-hetero[3]arene crystal material, the temperature of the vacuum heating is 45°C, and the time of the vacuum heating is 30min.

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