Inorganic fluorine-containing anion-functionalized microporous materials, methods of making and applications thereof
Patent Information
- Application Number
- CN202411727293.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-28
- Publication Date
- 2026-09-18
- Estimated Expiration
- 2044-11-28
AI Technical Summary
然而，目前还未有人报道过同时引入无机含氟阴离子与氮唑配体以构筑材料并应用于烯烃烷烃分离以及碳捕集应用
[0038] This invention introduces inorganic fluorine-containing anions and modifies the type and structure of nitrazole ligands to construct microporous materials and regulate functional sites, thereby obtaining abundant anion and nitrazole adsorption sites. It achieves effective recognition and differentiation of olefin or alkane molecules through differences in pore size and interaction forces. In particular, the inorganic fluorine-containing anions and nitrazole sites differentiate olefins and alkanes through electronic effects, thereby achieving selective separation of ethylene/ethane.
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Figure CN119570055B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of porous material synthesis and gas separation technology, specifically to a class of inorganic fluorine-containing anion-functionalized microporous materials, their preparation methods, and applications. Background Technology
[0002] Currently, the separation of high-purity gases and carbon capture are popular industrial research areas. Low-carbon hydrocarbons (including ethylene) are important basic chemical raw materials, widely used in various fields of manufacturing such as plastics, rubber, and masks, with huge demand. Industrially, multi-step separation methods such as catalytic dehydrogenation are commonly used, but the conversion rate is limited when preparing low-carbon olefins, and a large amount of alkanes are inevitably introduced into the products. Currently, cryogenic distillation is a commonly used technology for separating low-carbon olefins / alkanes in industrial production. This traditional gas separation and purification technology has high energy consumption, large equipment investment, and complex processes, resulting in high energy consumption and operating costs. The energy consumption for separating and removing alkanes from olefins accounts for approximately 0.3% of global energy consumption. Therefore, the development of efficient, energy-saving, clean, and environmentally friendly ethylene / ethane separation technology is urgently needed. Carbon capture is not only one of the key technologies for the low-carbon utilization of fossil energy, but also a feasible technical solution for deep decarbonization in industries with difficult emission reduction, such as steel, cement, and chemicals. Currently, among the mainstream CO2 capture methods, cryogenic distillation and liquid absorption both face the challenge of high energy consumption. Therefore, there is an urgent need to develop new separation technologies to achieve low-energy-consumption and high-efficiency gas separation and carbon capture.
[0003] Adsorption separation technology based on porous materials does not involve phase change and is a highly efficient and energy-saving separation technology. Due to its advantages such as low energy consumption, low cost, simple industrial process, and high product purity, this technology can achieve high product purity and yield, and has enormous potential for industrial applications.
[0004] For example, current olefin / alkane adsorption separation methods mainly fall into two categories: target gas preferential adsorption and impurity gas preferential adsorption. The adsorption-desorption process of the target gas preferential adsorption separation method is relatively complex, while the impurity gas preferential adsorption method can directly collect high-purity target gas in one step, with a simpler process, making it a more ideal method for high-purity gas production. For the separation and production of olefins and alkanes, preferential adsorption of alkanes is clearly a simpler and more efficient method. The core of the development and breakthroughs in adsorption separation technology based on porous materials lies in the design and synthesis of novel, highly efficient porous materials, which ideally possess high adsorption selectivity and excellent adsorption and separation capabilities. Among these, porous coordination polymers such as metal-organic frameworks (MOFs), molecular sieves, covalent organic frameworks (COFs), and hydrogen-bonded organic frameworks (HOFs) have attracted widespread attention due to their excellent performance in olefin and alkane separation and efficient carbon capture. For example, Zhang et al. designed and synthesized a fluorine-containing anion-supported material, ZU-36-Ni, which is composed of the metal ion Ni...+ Inorganic anion GeF6 2- It coordinates with the organic ligand pyrazine to form a highly efficient olefin / alkane separation. Its IAST separation selectivity for an ethylene / ethane (50 / 50) mixture at 298 K and 1 bar is 2.5 [Zhang Z, Ding Q, Cui X, et al. Fine-Tuning and Selective-Binding within an Anion-Functionalized Ultramicroporous Metal-OrganicFramework for Efficient Olefin / Paraffin Separation[J].ACS Applied Materials & Interfaces, 2020, 12(36):40229-35.]; Ding et al. reported an inorganic oxygen-containing anion-functionalized material ZnAtzPO4, which showed an equilibrium adsorption capacity of 1.92 mmol g for ethylene at 298 K and 1 bar. -1 The selectivity for ethylene / ethane separation was 12.4% [Ding Q, Zhang Z, Yu C, et al. Exploiting equilibrium-kinetic synergetic effect for separation of ethylene and ethane in a microporous metal-organic framework[J]. Science Advances, 2020, 6(15): eaaz4322.]. These microporous materials have also been reported to perform well in carbon capture, exhibiting high carbon dioxide adsorption capacity. However, no one has yet reported on the simultaneous introduction of inorganic fluorine-containing anions and azole ligands to construct materials for application in olefin and alkane separation and carbon capture.
[0005] In summary, the separation of ethylene and ethane still faces significant challenges. Furthermore, preferential adsorption of alkanes can directly remove alkane impurities from olefins, yielding high-purity olefin products, making it a more ideal method for alkane separation and removal. Moreover, for efficient carbon dioxide capture, there is an urgent need to develop high-performance adsorption and separation materials to improve the efficiency of the separation process. Summary of the Invention
[0006] To address the aforementioned technical problems and shortcomings in this field, this invention provides a class of inorganic fluorine-containing anion-functionalized microporous materials, their preparation methods, and applications. The microporous materials of this invention possess suitable pore sizes (e.g., It has abundant fluorine-containing anion and nitrogen azole adsorption sites, which can be used as adsorbents to preferentially adsorb alkanes under low pressure in olefins / alkanes, and to achieve carbon dioxide adsorption and separation.
[0007] [1] An inorganic fluorine-containing anion-functionalized microporous material, which is a polymer formed by coordination of metal ion M, inorganic fluorine-containing anion A and nitrogen azole organic ligand L through a solvothermal reaction; the solvothermal reaction is carried out by a rotary oven or microwave reaction.
[0008] The nitrazole organic ligand L is selected from at least one of compounds having the structure shown in any of formulas (I)-(IV) below:
[0009]
[0010] In formula (I), R1 is selected from the following groups: -H, -NH2, -CH3;
[0011] In formulas (I) and (II), R2 is independently selected from the following groups: -H, -NH2, -CH3, -COOH, -SH, -F, -Br, -Cl, -OH, -NO2, -CF3;
[0012] The metal ion M can be selected from Zn. 2+ Ni 2+ Cu 2+ At least one of them;
[0013] The inorganic fluorine-containing anion A is selected from SiF6. 2- GeF6 2- TiF6 2- ,NbOF5 2- SnF6 2- ZrF6 2- At least one of them.
[0014] Furthermore, the pore size of the inorganic fluorine-containing anion-functionalized microporous material is...
[0015] Optionally, the microporous material can be a polymer formed by a solvothermal reaction coordination of metal ions M, inorganic fluorine-containing anions A and nitrogen-based organic ligands L in a molar ratio of (0.5-5):1:(1-10) (e.g., 1:1:4-8, etc.).
[0016] In some embodiments, the inorganic fluorine-containing anion-functionalized microporous material has a rod-shaped microstructure, and further, the rod length can be 5 to 20 micrometers and the rod width can be 1 to 5 micrometers.
[0017] [2] A method for preparing the inorganic fluorine-containing anion-functionalized microporous material described in [1] includes:
[0018] Prepare a mixture containing metal ion M, inorganic fluorine-containing anion A and nitrogen-based organic ligand L, and perform a solvothermal reaction to obtain a crude target product. The crude target product is washed, degassed and activated to obtain the inorganic fluorine-containing anion-functionalized microporous material.
[0019] The solvothermal reaction is performed using a rotary oven or microwave reaction.
[0020] The method for preparing the inorganic fluorine-containing anion-functionalized microporous material described in this invention [1] is a solvothermal reaction synthesis method, preferably a microwave reaction synthesis method.
[0021] [2] In the method described, the molar ratio of metal ion M, inorganic fluorine-containing anion A and nitrogen azole organic ligand L in the mixture can be (0.5-5):1:(1-10), for example 1:1:4-8, etc.
[0022] [2] The method wherein the solvent in the mixture may be water and an organic solvent. Further, the organic solvent may be one or more of methanol, n-butanol, ethanol, and N,N-dimethylformamide. The volume ratio of water to organic solvent in the mixture may be (5:1) to (1:5), for example, 1:1.
[0023] [2] The method wherein the temperature of the solvothermal reaction can be 100-200°C, and more preferably 160-180°C;
[0024] In some embodiments, [2] the solvothermal reaction can be performed in a rotary oven, and the corresponding reaction time can be 48 to 72 hours.
[0025] In some embodiments, [2] the solvothermal reaction can be a microwave reaction, the microwave reaction time can be 0.5 to 3 hours, and further can be 0.5 to 1.5 hours, such as 1 hour, etc., and the microwave power is preferably not more than 250W, such as 100W, etc.
[0026] [2] The method described herein may use water and methanol as the detergent.
[0027] [2] The degassing and activation conditions of the method may include: vacuuming at 50-120°C (e.g., 100°C, etc.), and the degassing and activation time may be 8-24h, or even 10-12h.
[0028] [1] The inorganic fluorine-containing anion-functionalized microporous material described above can be applied to the field of gas adsorption.
[0029] [3] The application of the inorganic fluorine-containing anion-functionalized microporous material described in [1] in the selective adsorption and separation of olefins / alkanes. The application uses the inorganic fluorine-containing anion-functionalized microporous material as an adsorbent for the adsorption and separation of mixed gases containing olefins / alkanes. The olefins may include ethylene, etc. The alkanes may include ethane, etc.
[0030] [3] In the application described above, the volume ratio of olefin component to alkane component in the olefin / alkane mixed gas can be (1:99) to (99:1); the adsorption temperature can be -50 to 100℃; and the adsorption pressure can not exceed 10 bar.
[0031] [3] In the aforementioned application, the inorganic fluorine-containing anion-functionalized microporous material can preferentially adsorb alkanes at low pressures of 0 to 0.8 bar (e.g., 0.15 bar).
[0032] [4] The application of inorganic fluorine-containing anion-functionalized microporous materials as described in [1] in carbon dioxide adsorption. The carbon dioxide adsorption temperature can be -50 to 100℃, and the carbon dioxide adsorption pressure can not exceed 10 bar.
[0033] [5] A method for adsorption separation of olefins / alkanes, using the inorganic fluorine-containing anion-functionalized microporous material described in [1] as an adsorbent, contacting the adsorbent with a mixed gas containing olefins / alkanes to achieve selective adsorption separation of olefins and alkanes. The mixed gas may be a mixed gas containing ethylene / ethane.
[0034] [5] The method described herein can be further selected and optimized by referring to the application described in [3].
[0035] [6] A method for adsorbing carbon dioxide using the inorganic fluorine-containing anion-functionalized microporous material described in [1].
[0036] [6] The method described herein can be further selected and optimized by referring to the application described in [4].
[0037] [1] The inorganic fluorine-containing anion-functionalized microporous material can be amorphous particles or spherical or cylindrical particles after molding.
[0038] This invention introduces inorganic fluorine-containing anions and modifies the type and structure of nitrazole ligands to construct microporous materials and regulate functional sites, thereby obtaining abundant anion and nitrazole adsorption sites. It achieves effective recognition and differentiation of olefin or alkane molecules through differences in pore size and interaction forces. In particular, the inorganic fluorine-containing anions and nitrazole sites differentiate olefins and alkanes through electronic effects, thereby achieving selective separation of ethylene / ethane.
[0039] Compared with the prior art, the beneficial effects of this invention are as follows:
[0040] 1) The inorganic fluorine-containing anion-functionalized microporous material prepared by this invention has excellent structural design and high tunability, high density of inorganic fluorine-containing anion and azole functional sites, and the pore size of the material can be precisely controlled according to the type of ligand.
[0041] 2) The inorganic fluorine-containing anion-functionalized microporous material designed and synthesized in this invention has good recognition and differentiation ability for ethylene, ethane and propylene, propane, and can effectively achieve preferential adsorption of alkanes and selective separation of alkenes / alkanes. The high density of inorganic fluorine-containing anions and azole functional sites is conducive to the selective recognition of gases, and it also has a certain capture ability for carbon dioxide.
[0042] 3) The preferred preparation method of this invention is microwave synthesis, which is green, simple and fast, and anion-functionalized azole-based microporous coordination polymer materials are easy to prepare. Attached Figure Description
[0043] Figure 1 The adsorption isotherms of ZnAtzSiF6 for ethylene and ethane at 298 K are shown in Example 1.
[0044] Figure 2 The ethylene / ethane IAST separation selectivity of ZnAtzSiF6 in Example 1 was calculated at 298 K;
[0045] Figure 3 The image shows the X-ray diffraction (PXRD) pattern of ZnAtzSiF6 powder in Example 1.
[0046] Figure 4 , Figure 5 Here is a scanning electron microscope (SEM) image of ZnAtzSiF6 from Example 1;
[0047] Figure 6 The adsorption isotherms of ZnAtzGeF6 for ethylene and ethane at 298 K are shown in Example 2.
[0048] Figure 7 X-ray diffraction pattern of ZnAtzGeF6 powder in Example 2;
[0049] Figure 8 The adsorption isotherms of ZnAttzSiF6 for ethylene and ethane at 298 K are shown in Example 3.
[0050] Figure 9 The adsorption isotherms of ZnAtzTiF6 for ethylene and ethane at 298 K are shown in Example 4.
[0051] Figure 10The adsorption isotherms of carbon dioxide on ZnAtzSiF6 in Example 1, ZnAtzGeF6 in Example 2, ZnAttzSiF6 in Example 3, and ZnAtzTiF6 in Example 4 are shown at 298 K. Detailed Implementation
[0052] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.
[0053] Example 1
[0054] According to the metal ion Zn 2+ fluoride-containing SiF6 2- The organic ligands were added in a molar ratio of 1:1:8. Zinc hexafluorosilicate hexahydrate (0.5 mmol) and 3-amino-1,2,4-triazole (4 mmol) were dissolved in a mixed solution of methanol (5 mL) and water (5 mL). The solution was then transferred to a 35 mL microwave reaction flask and reacted at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated hexafluorosilicate functionalized microporous material, which can be used as an adsorbent and named ZnAtzSiF6.
[0055] Example 1: Adsorption isotherms of the adsorbent for ethylene and ethane at 298 K are as follows: Figure 1 As shown; the IAST separation selectivity of ethylene / ethane calculated for the adsorbent in Example 1 at 298 K is as follows: Figure 2 As shown; the PXRD pattern of the adsorbent in Example 1 is shown below. Figure 3 As shown; SEM image of the adsorbent in Example 1 is shown. Figure 4 , Figure 5 As shown, the adsorbent has a rod-shaped microstructure with a length of 10.44 μm and a width of 2.42 μm; the adsorption isotherm of the adsorbent for carbon dioxide at 298 K in Example 1 is shown below. Figure 10 As shown.
[0056] The hexafluorosilicic acid-functionalized microporous material described above has an adsorption capacity of 2.50 mmol / g for carbon dioxide at 1 bar. -1 Its adsorption capacity for ethylene at 1 bar is 1.55 mmol g. -1 The adsorption capacity of ethane is 1.57 mmol g. -1 At 0.15 bar, the ethane / ethylene (10 / 90 volume ratio) selectivity is 1.83, exhibiting preferential adsorption of alkanes at low pressure.
[0057] Example 2
[0058] According to the metal ion Zn2+ fluoride-containing GeF6 2- The organic ligands were added in a molar ratio of 1:1:8. Zinc nitrate hexahydrate (0.5 mmol), ammonium hexafluorogermanate (0.5 mmol), and 3-amino-1,2,4-triazole (4 mmol) were dissolved in a mixed solution of methanol (5 mL) and water (5 mL). The solution was then transferred to a 35 mL microwave reaction flask and reacted at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated hexafluorogermanate functionalized microporous material, which can be used as an adsorbent and named ZnAtzGeF6.
[0059] Example 2: Adsorption isotherms of the adsorbent for ethylene and ethane at 298 K are as follows: Figure 6 As shown; the PXRD pattern of the adsorbent in Example 2 is shown below. Figure 7 As shown; Example 2: Adsorption isotherm of carbon dioxide by the adsorbent at 298 K is shown below. Figure 10 As shown.
[0060] The hexafluorogermanic acid-functionalized microporous material described above has an adsorption capacity of 2.27 mmol / g for carbon dioxide at 1 bar. -1 Its adsorption capacity for ethylene at 1 bar is 1.45 mmol g. -1 The adsorption capacity of ethane is 1.48 mmol g. -1 At 0.15 bar, the ethane / ethylene (10 / 90 volume ratio) selectivity is 1.78, exhibiting preferential adsorption of alkanes.
[0061] Example 3
[0062] According to the metal ion Zn 2+ fluoride-containing SiF6 2- The organic ligands were added in a molar ratio of 1:1:8. Zinc hexafluorosilicate hexahydrate (0.5 mmol) and 5-aminotetrazole (4 mmol) were dissolved in a mixed solution of methanol (5 mL) and water (5 mL), and then transferred to a 35 mL microwave reaction flask. The reaction was carried out at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated hexafluorosilicate functionalized microporous material, which can be used as an adsorbent and named ZnAttzSiF6.
[0063] Example 3: Adsorption isotherms of the adsorbent for ethylene and ethane at 298 K are as follows: Figure 8 As shown, the adsorption isotherm of the adsorbent for carbon dioxide at 298 K in Example 3 is as follows: Figure 10 As shown, its adsorption capacity for carbon dioxide at 1 bar is 2.16 mmol / g.-1 Its adsorption capacity for ethylene at 1 bar is 1.30 mmol g. -1 The adsorption capacity of ethane is 1.36 mmol g. -1 At 0.15 bar, the ethane / ethylene (10 / 90 volume ratio) selectivity is 2.07, exhibiting preferential adsorption of alkanes.
[0064] Example 4
[0065] According to the metal ion Zn 2+ fluoride-containing TiF6 2- The organic ligands were added in a molar ratio of 1:1:4. Basic zinc carbonate (1 mmol), ammonium hexafluorotitanate (1 mmol), and 3-amino-1,2,4-triazole (4 mmol) were dissolved in a mixed solution of methanol (5 mL) and water (5 mL). The solution was then transferred to a 35 mL microwave reaction flask and reacted at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated hexafluorotitanate-functionalized microporous material, which can be used as an adsorbent and named ZnAtzTiF6.
[0066] Example 4: Adsorption isotherms of the adsorbent for ethylene and ethane at 298 K are as follows: Figure 9 As shown, the adsorption isotherm of the adsorbent for carbon dioxide at 298 K in Example 4 is as follows: Figure 10 As shown, its adsorption capacity for carbon dioxide at 1 bar is 1.78 mmol / g. -1 Its adsorption capacity for ethylene at 1 bar is 1.22 mmol g. -1 The adsorption capacity of ethane is 1.26 mmol g. -1 At 298 K and 0.15 bar, the ethane / ethylene (10 / 90 volume ratio) selectivity is 1.49, exhibiting preferential adsorption of alkanes.
[0067] Example 5
[0068] According to the metal ion Cu 2+ fluoride-containing SiF6 2- The organic ligands were added in a molar ratio of 1:1:8. Copper hexafluorosilicate (0.5 mmol) and 3-amino-1,2,4-triazole (4 mmol) were dissolved in a mixed solution of methanol (5 mL) and water (5 mL), and then transferred to a 35 mL microwave reaction flask. The reaction was carried out at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated hexafluorosilicate functionalized microporous material, which can be used as an adsorbent and named CuAtzSiF6.
[0069] Example 5: The adsorbent's ethylene adsorption capacity at 298 K and 1 bar was 1.35 mmol g. -1 The adsorption capacity of ethane is 1.39 mmol g. -1 At 0.15 bar, the ethane / ethylene (10 / 90 volume ratio) selectivity is 1.44, indicating that it preferentially and selectively adsorbs ethane when applied to ethylene / ethane separation.
[0070] Example 6
[0071] According to the metal ion Zn 2+ fluoride-containing SiF6 2- The organic ligands were added in a molar ratio of 1:1:8. Zinc hexafluorosilicate hexahydrate (0.5 mmol) and 3-amino-5-carboxylic acid-1,2,4-triazole (4 mmol) were dissolved in a mixed solution of methanol (5 mL) and water (5 mL). The solution was then transferred to a 35 mL microwave reaction flask and reacted at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated hexafluorosilicate functionalized microporous material, which can be used as an adsorbent and named ZnAtzcSiF6.
[0072] Example 6: The adsorbent's ethylene adsorption capacity at 298 K and 1 bar was 1.41 mmol g. -1 The adsorption capacity of ethane is 1.48 mmol g. -1 The selectivity for ethane / ethylene (10 / 90 volume ratio) at 0.15 bar is 1.51, indicating that it preferentially and selectively adsorbs ethane when used for ethylene / ethane separation.
[0073] Example 7
[0074] According to the metal ion Zn 2+ fluoride-containing SiF6 2- The organic ligands were added in a molar ratio of 1:1:4. Zinc hexafluorosilicate hexahydrate (1 mmol) and 4-(4H-1,2,4-triazol-4-yl)-4H-1,2,4-triazolium (4 mmol) were dissolved in a mixed solution of methanol (5 mL) and water (5 mL). The solution was then transferred to a 35 mL microwave reaction flask and reacted at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated hexafluorosilicate functionalized microporous material, which can be used as an adsorbent and named ZnBtzSiF6.
[0075] Example 7: The adsorbent's ethylene adsorption capacity at 298 K and 1 bar was 1.36 mmol g. -1The adsorption capacity of ethane is 1.42 mmol g. -1 At 0.15 bar, the selectivity for ethane / ethylene (10 / 90 volume ratio) is 1.38, indicating that it preferentially and selectively adsorbs ethane when applied to ethylene / ethane separation.
[0076] Example 8
[0077] According to the metal ion Ni 2+ fluoride NbOF5 2- Nickel pentafluoroniobate (1 mmol) and 3-amino-1,2,4-triazole (4 mmol) were added in a 1:1:4 molar ratio with organic ligands. The solutions were dissolved in a mixture of methanol (5 mL) and water (5 mL) and then transferred to a 35 mL microwave reaction flask. The mixture was reacted at 100 W microwave power and 180 °C for 1 h to obtain a white solid precipitate. The precipitate was filtered, washed with water and methanol, and finally activated under vacuum at 100 °C for 10 h to obtain activated pentafluoroniobate-functionalized microporous material, which can be used as an adsorbent and named NiAtzNbOF5.
[0078] Example 8: The adsorbent's ethylene adsorption capacity at 298 K and 1 bar was 1.31 mmol g. -1 The adsorption capacity of ethane is 1.38 mmol g. -1 At 0.15 bar, the selectivity for ethane / ethylene (10 / 90 volume ratio) is 1.35, indicating that it preferentially and selectively adsorbs ethane when applied to ethylene / ethane separation.
[0079] Comparative Example 1
[0080] Comparative Example 1 synthesized SIFSIX-2-Cu-i, a reported material (Science 353, 141-144 (2016)), using a microwave reactor. SIFSIX-2-Cu-i is a microporous material composed of metal ions, fluoride ions, and pyridine compounds, differing from Example 2 in the use of metal ions and organic ligands. The microporous material adsorbent of Comparative Example 1 exhibited an ethylene adsorption capacity of 2.53 mmol g at 298 K and 1 bar. -1 The adsorption capacity of ethane is 1.81 mmol g. -1 Compared with Example 2, it cannot achieve the separation of alkanes and olefins under low pressure (0-0.8 bar) and does not have the characteristic of preferentially adsorbing alkanes.
[0081] Comparative Example 2
[0082] Comparative Example 2 is the inorganic fluorine-containing microporous anion exchange material SIFSIX-3-Zn, which has been reported in the literature (CrystEngComm 22(2020)2649-2655.). The difference between Comparative Example 2 and Example 2 is that its organic ligand is pyrazine. The only reported ethylene adsorption capacity of the inorganic fluorine-containing microporous anion exchange material in Comparative Example 2 is 2.24 mmol g at 298 K. -1 Compared with Example 2, the data shows that it cannot separate alkanes and olefins, and it does not have the characteristic of preferentially adsorbing alkanes.
[0083] Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.
Claims
1. The application of inorganic fluorine-containing anion-functionalized microporous materials in the selective adsorption and separation of olefins / alkanes, characterized in that, The inorganic fluorine-containing anion-functionalized microporous material is used as an adsorbent for the adsorption and separation of mixed gases containing olefins / alkanes; the olefin is ethylene; the alkane is ethane; the inorganic fluorine-containing anion-functionalized microporous material preferentially adsorbs alkanes under low pressure (0~0.8 bar); This microporous material is a polymer formed by the coordination of metal ions M, inorganic fluorine-containing anions A, and nitrogen-azole organic ligands L through a solvothermal reaction; the solvothermal reaction is carried out in a rotary oven or microwave reaction; the inorganic fluorine-containing anion functionalized microporous material has a rod-shaped micromorphology with a rod length of 5-20 micrometers and a rod width of 1-5 micrometers; The nitrazole organic ligand L is selected from at least one of compounds having the structure shown in any of the following formulas (I)-(IV): In formula (I), R1 is selected from the following groups: -H, -NH2, -CH3; In formulas (I) and (II), R2 is independently selected from the following groups: -H, -NH2, -CH3, -COOH, -SH, -F, -Br, -Cl, -OH, -NO2, -CF3; The metal ion M is selected from Zn. 2+ Ni 2+ Cu 2+ At least one of them; The inorganic fluorine-containing anion A is selected from SiF6. 2- GeF6 2- TiF6 2- ,NbOF5 2- SnF6 2- ZrF6 2- At least one of them.
2. The application according to claim 1, characterized in that, The pore size of the inorganic fluorine-containing anion-functionalized microporous material is 3~7 Å. The inorganic fluorine-containing anion-functionalized microporous material is a polymer formed by the coordination of metal ion M, inorganic fluorine-containing anion A and nitrogen-azole organic ligand L through a solvothermal reaction in a molar ratio of (0.5~5):1:(1~10).
3. The application according to claim 1 or 2, characterized in that, The method for preparing the inorganic fluorine-containing anion-functionalized microporous material includes: Prepare a mixture containing metal ion M, inorganic fluorine-containing anion A and nitrogen-based organic ligand L, and perform a solvothermal reaction to obtain a crude target product. The crude target product is washed, degassed and activated to obtain the inorganic fluorine-containing anion-functionalized microporous material. The solvothermal reaction is performed using a rotary oven or microwave reaction.
4. The application according to claim 3, characterized in that, In the mixture, the molar ratio of metal ion M, inorganic fluorine-containing anion A, and nitrogen-based organic ligand L is (0.5~5):1:(1~10); The solvent in the mixture is water and an organic solvent; In the solvent of the mixture, the volume ratio of water to organic solvent is (5:1) to (1:5); The organic solvent is one or more of methanol, n-butanol, ethanol, and N,N-dimethylformamide.
5. The application according to claim 3, characterized in that, The temperature of the solvothermal reaction is 100~200℃; The solvothermal reaction is carried out in a rotary oven with a reaction time of 48-72 hours; or the solvothermal reaction is carried out in a microwave oven with a reaction time of 0.5-3 hours and a microwave power of no more than 250 W. The washing process uses water and methanol as detergents. The degassing and activation conditions include: vacuuming at 50~120℃ and degassing and activation time of 8~24 h.
6. The application according to claim 5, characterized in that, The temperature of the solvothermal reaction is 160~180℃; The microwave reaction time is 0.5~1.5 h.
7. The application according to claim 1, characterized in that, The volume ratio of olefin components to alkane components in the olefin / alkane mixture is (1:99) to (99:1); the adsorption temperature is -50 to 100℃; and the adsorption pressure does not exceed 10 bar.