CN114644760A - Preparation and gas separation application of copper-based microporous metal organic framework material - Google Patents
Preparation and gas separation application of copper-based microporous metal organic framework material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 239000010949 copper Substances 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013336 microporous metal-organic framework Substances 0.000 title claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 47
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 45
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 25
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 24
- 239000013110 organic ligand Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000001530 fumaric acid Substances 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000013084 copper-based metal-organic framework Substances 0.000 claims abstract description 10
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
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- 239000005977 Ethylene Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
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- 238000009835 boiling Methods 0.000 claims description 2
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- 150000001879 copper Chemical class 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000005431 greenhouse gas Substances 0.000 claims description 2
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims 1
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 1
- 229940045803 cuprous chloride Drugs 0.000 claims 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 2
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
A preparation and gas separation application of a copper-based microporous metal organic framework material belongs to the technical field of crystalline porous material preparation and gas separation. The organic ligand fumaric acid and the copper nitrate are prepared under the solvothermal condition. The Cu-MOF structure has high porosity, a unique cylindrical one-dimensional pore canal exists in the framework, and the inner wall of the pore canal is distributed with open metal sites and electronegative oxygen atoms, thereby providing action sites for the adsorption process of a plurality of gases. A plurality of tests show that: the Cu-MOF material has strong interaction force with acetylene gas molecules and weaker interaction force with carbon dioxide molecules, so that the high-efficiency selective adsorption and separation of acetylene/carbon dioxide mixed gas are realized. Finally, the acetylene purification task is completed in the adsorption and desorption cycle process, and the energy consumption in the separation process is obviously reduced. In addition, the Cu-MOF material can realize amplified preparation in a certain range and has short synthesis period, thereby having great industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of crystalline porous material preparation and gas separation, and particularly relates to a novel copper-based microporous Metal Organic Framework (MOF) material and a preparation method thereof.
Background
Acetylene gas is one of the important basic raw materials in the production of petrochemical industry and electronic industry, and is generally used for manufacturing products such as acetaldehyde, acetic acid, benzene, synthetic rubber and the like. Further, acetylene gas can also be used as the illumination gas and the welding gas. Crude acetylene is generally obtained industrially by hydrocarbon pyrolysis processes, and the crude product often contains a large amount of by-products, including carbon dioxide. Since acetylene and carbon dioxide molecules have similar boiling points (-84 ℃ and-78.5 ℃), similar three-dimensional dimensions and the same kinetic diameter
It is very difficult to realize the high-efficiency separation and purification of the two. Meanwhile, acetylene gas is sensitive to physical factors such as heat, pressure and the like, and explosion can occur when the compression pressure is more than 0.2MPa under the room temperature and oxygen-free conditions, so that the acetylene purification process in industrial production faces a plurality of challenges. In the traditional industry, the acetylene/carbon dioxide mixed gas is separated mainly by adopting a low-temperature rectification technology with high energy consumption, and the related separation equipment has large investment and complex maintenance. Therefore, developing a new acetylene/carbon dioxide separation technology and optimizing the existing separation process are of great significance to the acetylene industry. Due to the advantages of relatively low energy consumption, high separation selectivity, simple process and the like, the adsorption separation technology based on the porous material is expected to solve a plurality of problems in the traditional separation process and bring a new opportunity for acetylene purification. The core of the adsorption separation technology lies in developing and preparing a high-efficiency porous adsorption material to selectively capture acetylene or carbon dioxide, and then carrying out material butt joint and process coupling with a chemical process to complete the development of a new separation and purification process.
Metal Organic Frameworks (MOFs) are a new crystalline porous functional material, which is a multi-element Metal/Metal cluster node or organic ligand based on coordination bondA pore-net skeleton structure material. The MOFs material has wide application prospect in the fields of adsorption separation, gas storage, drug slow release, heterogeneous catalysis and the like because the MOFs material has the characteristics of high porosity, large specific surface area, adjustable pore size and pore surface physicochemical environment and the like on the structure. In recent years, many MOFs have been used for adsorption separation of lower hydrocarbons, such as ethane/ethylene, acetylene/ethylene to purify ethylene, propane/propylene, and propyne/propylene to purify propylene, including acetylene/carbon dioxide separation. Although many research results show that the MOFs has unique advantages and obtains good effects when being used as an adsorbent material to separate a low-carbon hydrocarbon mixture, how to consider high separation selectivity, relatively low preparation cost and relatively high synthesis efficiency is still one of the difficulties faced in the screening and preparation of acetylene/carbon dioxide adsorption separation materials. The invention adopts a cheap and easily obtained dicarboxylic acid organic ligand fumaric acid (fumaric acid, corynic acid, H)2Fuma) self-assemble with copper nitrate under solvothermal conditions to form a microporous copper-based MOF material. The MOF crystal structure has high porosity and one-dimensional pore channels, and open metal sites and electronegative oxygen atoms distributed in the pore channels provide action sites for the adsorption of acetylene and carbon dioxide gas molecules. In addition, the material shows preferential adsorption to acetylene gas in a single-component static adsorption test and an acetylene/carbon dioxide mixed gas dynamic penetration test, so that the aim of efficiently purifying acetylene in adsorption and desorption cycles is fulfilled.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-based microporous MOF material (Cu-MOF) constructed based on cheap and easily-obtained ligands, which can be used for efficiently separating acetylene/carbon dioxide mixed gas, can complete preparation in a short time and is convenient for large-scale synthesis.
A copper-based microporous metal organic framework material is characterized in that the copper-based microporous metal organic framework material, namely a Cu-MOF material, is used as an organic ligand and is reacted with copper salt through a solvothermal method to prepare a light blue flaky crystal material, and the chemical formula of the material is C11H15Cu3NO12Is divided intoHas a sub-formula of [ Cu3(Fuma)2(OH)2]·DMF·H2O，H2Fuma is fumaric acid.
The Cu-MOF material belongs to a monoclinic system by analyzing from the perspective of a crystal structure, and has a space group of P21And c, unit cell parameters are as follows:
α＝90°，β＝114.502(2)°，γ＝90°，
the Cu metal center in the Cu-MOF is in a penta-coordination or hexa-coordination mode, and the coordination geometrical configuration is octahedron or tetrahedron. The carboxyl oxygen atoms in the fumaric acid ligand participate in coordination; in addition, hydroxyl species generated in the material synthesis are coordinated with Cu and play a bridging role. And finally, the carboxyl and the hydroxyl are coordinated with the Cu metal center together to form chain-shaped Secondary Building Units (SBUs) which are alternately arranged according to a certain rule. Adjacent SBUs are connected through a fumaric acid ligand to form a two-dimensional layered structure; the layered structures are also expanded into a final three-dimensional framework structure through the connection of organic ligands. The three-dimensional framework of the Cu-MOF comprises a one-dimensional cylindrical channel structure, and free N, N-Dimethylformamide (DMF) solvent molecules are regularly filled in one-dimensional pore channels of the Cu-MOF.
The synthesis method of the Cu-MOF material mainly comprises the following steps: reacting an organic ligand fumaric acid (H)2Fuma) and a copper source are dissolved into a mixed solution of N, N-Dimethylformamide (DMF), acetonitrile, fluoroboric acid and water, and then the final light blue flaky Cu-MOF product is obtained through solvothermal reaction under a closed condition.
The molar ratio of the organic ligand to the copper in the technical scheme is 1: (1-10); the volume ratio of DMF, acetonitrile and water in the mixed solvent is 4: (1-5): (1-5); the volume ratio of the fluoboric acid dosage to the mixed solution is 1: 60 to 300. The solvent thermal reaction temperature is 70-120 ℃, and the reaction time is 0.5-10 h.
The selected copper source is one or more of copper acetate, copper nitrate, copper sulfate and copper chloride, and preferably copper nitrate.
After the obtained Cu-MOF material is washed by DMF, a final separation material for efficiently and selectively separating acetylene and carbon dioxide mixed gas is obtained after solvent exchange and vacuum removal of guest molecules (the process is called sample activation), and acetylene is preferentially adsorbed in the separation process.
The method is used for selectively separating acetylene and carbon dioxide mixed gas, acetylene and ethylene mixed gas, propylene and propane mixed gas or other low-carbon hydrocarbons and related gas mixtures such as greenhouse gases, energy gases and the like.
The invention discloses a microporous copper-based MOF material prepared by self-assembly of a dicarboxylic acid ligand and metal copper ions, which is cheap, easy to obtain and simple in structure. The material has the specific beneficial effects that:
(1) organic ligand fumaric acid (H) used in material synthesis2Fuma) has simple structure, rich industrial sources and low market price, and is beneficial to reducing the raw material cost in the synthesis of the Cu-MOF material. Meanwhile, the ligand has rich coordination modes, two carboxyl groups in the ligand can be self-assembled with metal nodes to form various SBUs, and the structural form of the final MOFs material is greatly expanded.
(2) A large number of coordination unsaturated metal sites and electronegative oxygen atoms exist on the inner surface of the pore channel of the finally obtained Cu-MOF material, and can generate stronger pi complexation or hydrogen bond interaction with gas molecules. In addition, the cylindrical one-dimensional channel in the structure provides a structural basis for the diffusion mass transfer process of different gases.
(3) Multiple host-guest interactions exist between adsorption sites regularly arranged in the pore channels and acetylene gas molecules, and the acting force of the acetylene gas molecules and the framework is enhanced, so that the effect of preferentially adsorbing acetylene gas in acetylene/carbon dioxide mixed gas is realized, the acetylene purification task is completed in adsorption and desorption cycles, and the energy consumption in the separation process is obviously reduced.
(4) The Cu-MOF material is a product with stable dynamics, can complete synthesis and preparation in a short time, has the synthesis efficiency remarkably higher than that of most MOFs materials, can expand a reaction system in a certain range, realizes amplified preparation, and lays a foundation for industrial mass production.
(5) The Cu-MOF material has high porosity and diversified adsorption sites, and has application potential in other gas separation systems besides being applied to the separation of acetylene/carbon dioxide mixed gas.
Drawings
FIG. 1 is a schematic representation of the three-dimensional crystal structure of a Cu-MOF of the present invention.
FIG. 2 is a photograph of an optical photograph of a Cu-MOF sample according to the present invention.
FIG. 3 is a powder diffraction pattern of a freshly synthesized sample and an adsorption-tested sample of Cu-MOF in accordance with single crystal structure data simulation of the present invention.
FIG. 4 shows N of Cu-MOF under 77K condition in the present invention2Adsorption and desorption graphs.
FIG. 5 is a graph showing single-component adsorption of acetylene and carbon dioxide under 298K conditions by Cu-MOF in the present invention.
FIG. 6 is a schematic illustration of IAST selectivity of Cu-MOF of the present invention in 298K for separation of acetylene/carbon dioxide (50/50) mixture.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The first step is as follows: 10mg of fumaric acid organic ligand, 30mg of copper nitrate hexahydrate were weighed and dissolved in 2mL of N, N-Dimethylformamide (DMF), 1mL of acetonitrile and 1mL of water. After sonication and obtaining a homogeneous solution, the solution was then transferred to a 10mL glass reaction flask, 0.025mL of fluoroboric acid was added, and the mixture was reacted at 100 ℃ for 0.5h to obtain a light blue flake crystalline sample of Cu-MOF in a yield of 80% (based on the organic ligand).
The second step is that: selecting a single crystal sample with proper size and good crystallization, collecting diffraction data by using a single crystal diffractometer under the condition of 298K, and refining by using a related structure analysis program to obtain a crystal structure. The specific structure is shown in the attached drawings of the specification. The purity of the bulk preparation samples was confirmed by X-ray powder diffraction techniques.
The third step: in order to remove DMF molecules as a solvent in pores of the material, the obtained material sample is soaked in an anhydrous methanol solvent after being washed by DMF for multiple times. The solvent exchange process was continued for 5 days with daily replacement of fresh methanol solvent. Finally, the mixture was treated 3 times with anhydrous dichloromethane as an exchange solvent. And degassing the sample subjected to solvent exchange at 120 ℃ for 8h under vacuum to prepare the material for testing gas adsorption.
The fourth step: before the single-component static adsorption test, the materials are loaded into an adsorption tube and degassed at 80 ℃ for 2h again, and then acetylene and carbon dioxide adsorption curve data at 298K are collected.
The three-dimensional structure of the crystal in fig. 1 shows: two carboxyl groups on an organic ligand in the Cu-MOF are coordinated with a Cu metal center, and the coordination geometrical configuration comprises an octahedron and a tetrahedron. Hydroxyl groups generated in the reaction process are coordinated with Cu and form an infinitely extended chain SBU together with carboxyl. Meanwhile, a unique one-dimensional cylindrical channel exists in the structure, and free DMF molecules are regularly filled in the pore channel.
The photo-optic diagram in fig. 2 shows: the Cu-MOF crystalline sample has large macroscopic size, light blue color and flaky shape.
The powder diffraction pattern in fig. 3 shows: the freshly prepared Cu-MOF sample has good crystallization and good purity. Meanwhile, the sample after the adsorption test still keeps good crystallinity, and the structure is not obviously changed. It is noted that the reason why the diffraction peaks of the sample part do not coincide with the simulated spectrum is that the sample exhibits a high degree of preferred orientation during the crystallization process.
The nitrogen adsorption curve in fig. 4 shows: Cu-MOF N at 77K2The adsorption is represented by a classic I-shaped curve, and corresponds to a one-dimensional micropore channel in the structure, so that the structural basis of the material for realizing gas adsorption is further proved.
The acetylene carbon dioxide single component adsorption curve in fig. 5 shows: Cu-MOF has higher adsorption capacity to two gases, and meanwhile, the action force of the framework and acetylene gas molecules is stronger, specifically 298K, and the acetylene adsorption capacity is larger under the same pressure of a low-pressure area (lower than 200 mmHg). The phenomenon lays a foundation for applying the material to separation and purification of acetylene/carbon dioxide mixed gas.
Example 2
100mg of fumaric acid organic ligand, 300mg of copper nitrate hexahydrate were weighed and dissolved in 20mL of N, N-Dimethylformamide (DMF), 10mL of acetonitrile and 10mL of water. After sonication and obtaining a homogeneous solution, the solution was transferred to a 100mL glass reaction flask, 0.25mL of fluoroboric acid was added, and the mixture was reacted at 100 ℃ for 2h to obtain a light blue flake crystalline sample of Cu-MOF in a 75% yield (based on the organic ligand).
The results of the above embodiments show that the microporous Cu-MOF material has a remarkable one-dimensional channel space structure, abundant and various adsorption sites, higher adsorption capacity for acetylene and carbon dioxide gases, and excellent separation performance for the mixed gas of the acetylene and the carbon dioxide gases. In addition, the ligand involved in the material has low cost, short synthesis process time and easy amplification preparation, and has great industrial application potential. The invention not only provides a high-efficiency adsorbent material for separating acetylene/carbon dioxide mixed gas, but also provides an important material for exploring the structure-activity relationship of the metal organic framework material applied to the field of gas separation.
The foregoing is a preferred embodiment of the present invention, but the present invention should not be limited to the disclosure of this embodiment. Therefore, equivalents and modifications may be made thereto without departing from the spirit of the disclosure.
Claims (10)
1. The copper-based microporous metal organic framework material is characterized in that the copper-based microporous metal organic framework material is a Cu-MOF material, and the chemical formula of the Cu-MOF material is C11H15Cu3NO12Molecular formula is [ Cu ]3(Fuma)2(OH)2]·DMF·H2O，H2Fuma is fumaric acid.
2. A copper-based microporous metal organic framework material according to claim 1, whereinThe cell parameters are as follows:
α is 90 °, β is 114.502(2 °), and γ is 90 °. The crystal is monoclinic, and the space group is P21/c。
3. The copper-based microporous metal organic framework material according to claim 1, wherein the Cu metal center in the Cu-MOF is in a hexacoordinate or pentacoordinate mode, and two carboxylic acid groups in an organic ligand and a hydroxyl group generated in the reaction participate in coordination; chain-like Secondary Building Units (SBUs) consisting of carboxyl oxygen, hydroxyl oxygen and Cu metal nodes exist in the structure; adjacent SBUs are connected through organic ligands to form a two-dimensional layered structure, and the layered structures are also connected through ligands to form a final three-dimensional framework structure. A one-dimensional cylindrical pore canal exists in the skeleton structure, and the inner wall of the pore canal is modified by high-density open metal sites and electronegative oxygen atoms; solvent molecules DMF introduced in the material synthesis are regularly filled in the one-dimensional pore channels.
4. A method for preparing a copper-based microporous metal organic framework material according to any one of claims 1 to 3, comprising the steps of:
preparation of Cu-MOF: reacting an organic ligand fumaric acid (H)2Fuma) and a copper source are dissolved in a mixed solvent of N, N-Dimethylformamide (DMF), acetonitrile, fluoroboric acid and water, ultrasonic oscillation and stirring are carried out, the solvothermal reaction is carried out under the closed condition, the reaction temperature is 70-120 ℃, the reaction time is 0.5-10 h, and after the crystalline material is prepared, the crystalline material is soaked and washed by DMF and the like.
5. The method according to claim 4, characterized in that in the step (A), the solvothermal reaction conditions are preferably 100 ℃, and the constant temperature is preferably 1 h; the ratio of the organic ligand to the copper source is 1: (1 to 10), preferably 1: 3;
the selected copper source is one or more of copper acetate, copper nitrate, copper sulfate, copper chloride and cuprous chloride or other copper salt, preferably copper nitrate.
6. The method according to claim 4, wherein in the step (A), the volume ratio of DMF, acetonitrile and water in the mixed solvent is 4: (1-5): (1-5), preferably 4: 1: 1.
7. the method according to claim 4, wherein the mixed solvent system in the synthesis step involves three or one or two of DMF, acetonitrile and water or other organic and inorganic solvents.
8. Use of the copper-based microporous metal organic framework material according to any one of claims 1 to 3 for selective separation of acetylene and carbon dioxide gas mixture, acetylene and ethylene gas mixture, propylene and propane gas mixture or other low carbon hydrocarbons and related gas mixtures such as greenhouse gases, energy gases and the like.
9. Use according to claim 8, wherein the Cu-MOF material is washed with DMF, and the resulting material after solvent exchange and vacuum removal of guest molecules is used as a final separation material for selective separation of acetylene/carbon dioxide gas mixtures, with preferential adsorption of acetylene during the separation process. Wherein the solvent used for the exchange is characterized by a small size and a low boiling point.
10. Use according to claim 8 or 9, wherein the separation conditions are 0 ℃ to 60 ℃ and 1 to 10 standard atmospheres; preferably 25 c, at one standard atmosphere.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1066864A (en) * | 1996-08-28 | 1998-03-10 | Osaka Gas Co Ltd | Method for recovering complex adsorbing chemical substance |
| CN103030655A (en) * | 2012-12-13 | 2013-04-10 | 浙江大学 | Microporous transition-group metal organic framework material, and preparation and application methods thereof |
| US20140061540A1 (en) * | 2011-03-07 | 2014-03-06 | The Regents Of The University Of California | Metal-organic framework adsorbents for composite gas separation |
| WO2019231297A1 (en) * | 2018-05-31 | 2019-12-05 | 한국화학연구원 | Novel metal-organic framework having porous structure formed from zirconium cluster secondary building unit and multi-binding linker |
| CN110938213A (en) * | 2019-12-19 | 2020-03-31 | 北京工业大学 | Preparation method of copper-based microporous metal organic framework material and gas separation application thereof |
| CN111072987A (en) * | 2019-12-19 | 2020-04-28 | 北京工业大学 | Two fluorinated metal organic framework materials, preparation and low-carbon hydrocarbon separation application thereof |
-
2020
- 2020-12-19 CN CN202011510010.1A patent/CN114644760A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1066864A (en) * | 1996-08-28 | 1998-03-10 | Osaka Gas Co Ltd | Method for recovering complex adsorbing chemical substance |
| US20140061540A1 (en) * | 2011-03-07 | 2014-03-06 | The Regents Of The University Of California | Metal-organic framework adsorbents for composite gas separation |
| CN103030655A (en) * | 2012-12-13 | 2013-04-10 | 浙江大学 | Microporous transition-group metal organic framework material, and preparation and application methods thereof |
| WO2019231297A1 (en) * | 2018-05-31 | 2019-12-05 | 한국화학연구원 | Novel metal-organic framework having porous structure formed from zirconium cluster secondary building unit and multi-binding linker |
| CN110938213A (en) * | 2019-12-19 | 2020-03-31 | 北京工业大学 | Preparation method of copper-based microporous metal organic framework material and gas separation application thereof |
| CN111072987A (en) * | 2019-12-19 | 2020-04-28 | 北京工业大学 | Two fluorinated metal organic framework materials, preparation and low-carbon hydrocarbon separation application thereof |
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