CN112156660A - Metal organic framework M-gate mixed matrix membrane and preparation and application thereof - Google Patents
Metal organic framework M-gate mixed matrix membrane and preparation and application thereof Download PDFInfo
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- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 57
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000004642 Polyimide Substances 0.000 claims abstract description 32
- 229920001721 polyimide Polymers 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010345 tape casting Methods 0.000 claims description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- -1 diamine compound Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention provides a metal organic framework M-gate mixed matrix membrane and preparation and application thereof. The mixed matrix membrane is formed by mixing M-gate particles and polyimide polymer; the mass of the M-gate particles accounts for 5-50% of the total mass of the M-gate particles and the polyimide. Wherein, M-gate is used as filling material, and polyimide polymer is used as substrate film material. M-gate mixed matrix membrane is prepared by dispersing M-gate particles and polyimide by organic solvent, blending the two physically and then blade-coating, and the separation application of the mixed matrix membrane in ethylene/ethane gas is developed.
Description
Technical Field
The invention belongs to the technical field of gas separation membranes, and particularly relates to a metal organic framework M-gate mixed matrix membrane, and preparation and application thereof.
Background
Olefin/alkane separation is an energy intensive process in industrial production and is considered by scientists as one of seven major chemical separation processes that can change the world. The low temperature distillation method is adopted in industry at present to achieve the purpose of separating olefin and alkane. However, because of the close boiling points of the two, the investment of production equipment is large, and the energy consumption in the separation process is high. The membrane separation technology has the advantages of low energy consumption, low cost, high packing density, simple operation and the like as a novel separation technology, thereby having great application potential in the aspect of olefin/alkane separation. Among them, the polymeric separation membrane has many advantages such as high physical and chemical stability, easy large-scale preparation and mild operation conditions, and has become a mainstream membrane material. Polyimide is obtained by reacting acid anhydride with diamine compound to form poly-amino acid, and then carrying out imidization reaction. The polymer is a high-strength engineering material with high temperature resistance and solvent resistance. Of these, Matrimid, which is commercialized, is the most commonly used polyimide material in recent years. In addition, the free volume of the polymer chain can be increased by selecting dianhydride (commonly known as 6FDA) containing trifluoromethyl group, and currently, polyimide based on 6FDA is one of the polymer membrane materials having the most excellent separation performance. However, polymer membranes have a conflicting relationship of permeability and selectivity (trade-off effect). Metal-organic frameworks (MOFs) are three-dimensional porous materials with characteristics of large specific surface area, adjustable pore channels, rich topological structures, and the like. The metal organic framework can be subjected to pore channel and functionalization modification according to a target separation system, so that the high-efficiency separation efficiency of the target separation system is realized. The mixed matrix membrane prepared by physically doping the metal organic framework material and the polymer can effectively improve the separation performance of the polymer membrane and break through the trade-off limit of a pure polymer membrane.
Disclosure of Invention
One purpose of the invention is to provide a metal organic framework M-gate mixed matrix membrane, and the other purpose of the invention is to provide a preparation method of the metal organic framework M-gate mixed matrix membrane; it is still another object of the present invention to provide a use of a metal organic framework M-gate mixed matrix membrane for C2H4/C2H6Separation of (4).
The technical scheme adopted by the invention is as follows: a metal organic framework M-gate mixed matrix membrane is characterized in that: the M-gate mixed matrix membrane is formed by mixing M-gate particles and a polyimide polymer; wherein the mass of the M-gap particles accounts for 5-50% of the total mass of the M-gap particles and the polyimide.
Preferably, the M-gate is Mg-gate, Ni-gate or Co-gate. Its synthesis scheme references: 10.1002/anie.201808716 (DOI).
Preferably, the polyimide polymer is a polyimide material synthesized by matrix or dianhydride (commonly known as 6FDA) monomer containing trifluoromethyl; wherein the polyimide material synthesized by the dianhydride monomer containing trifluoromethyl is 6FDA-DAM, 6FDA-Durene, 6FDA-DAM/DABA or 6 FDA-NDA/Durene. The polyimides are obtained by polycondensation and imidization between monomers. The monomers required for the reaction are directly available commercially. Polyimide synthesis can be referred to: 10.1016/j.memsci.2018.08.031 (DOI).
Preferably, the thickness of the mixed matrix film is in the range of 10 μm to 75 μm.
The invention also provides a method for preparing the metal organic framework M-gate mixed matrix membrane, which comprises the following steps:
a) weighing a polyimide polymer, mixing and stirring the polyimide polymer with an organic solvent to obtain a polyimide solution with the mass concentration of 7-20%;
b) weighing M-gate particles, adding the M-gate particles into an organic solvent, performing ultrasonic treatment, mixing and stirring to obtain M-gate dispersion liquid with the mass concentration of 0.5-6%;
c) respectively taking M-gate dispersion liquid and polyimide solution according to the mass of the M-gate particles accounting for 5% -50% of the total mass of the M-gate particles and the polyimide, and mixing and stirring to obtain uniformly dispersed membrane casting liquid;
d) a self-supporting M-gate mixed matrix membrane was obtained by means of knife coating. Namely, scraping the casting solution on a flat plate by using a scraping mode, drying at room temperature until the solvent is volatilized, and then placing in a vacuum drying oven for drying to obtain the M-gate mixed matrix membrane.
Preferably, the organic solvents described in steps a) and b) are all chloroform (CHCl)3) Dichloromethane (CH)2Cl2) Or Tetrahydrofuran (THF).
The invention also provides an application of the metal organic framework M-gate mixed matrix membrane in ethylene/ethane gas separation. The application is characterized in that: the mixed matrix membrane preferentially permeates C2H4To C2H4/C2H6The mixed gas has good selectivity, and the separation of high-pressure gas can be realized. The pressure range is 0.1MPa-2MPa, and the temperature range is 20-40 ℃.
Has the advantages that:
(1) selected M-gate material pair C2H4/C2H6The adsorption selectivity of the composite reaches more than 30, and the prepared defect-free mixed matrix membrane improves C2H4/C2H6The separation selectivity of (3);
(2) the selected porous structure of the M-gate can allow ethylene gas to permeate, the existence of the M-gate particles in the mixed matrix membrane provides more transmission channels for ethylene, and effectively prevents ethane molecules from permeating, and compared with a polyimide pure membrane, the permeability of the ethylene gas is greatly increased;
(3) the mixed matrix membrane prepared by the present invention shows higher gas permeability at high pressure and separation selectivity can be maintained at a higher level, compared to the pure polymer.
Drawings
FIG. 1 is an SEM cross-sectional view with an enlarged scale of 2 μm for 6FDA-DAM mixed matrix membranes of different Ni-gate doping amounts prepared in example 2, wherein (a) represents an SEM image of a pure 6FDA-DAM polymer membrane and (b) represents an SEM image of a mixed matrix membrane with a Ni-gate loading of 20 wt.%;
FIG. 2 is a graph of the long term stability test results of the 20 wt.% Co-gate/6 FDA-DAM mixed matrix membrane in example 5 in a 25 ℃ mixed gas separation.
Detailed Description
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the examples described below, and various implementations are included within the technical scope of the present invention within the content and scope of the present invention. Furthermore, references to the synthesis of Ni-gate, Co-gate and Mg-gate are cited in document 10.1002/anie.201808716 (DOI). Several polyimides used in mixed matrix membranes are obtained by polycondensation and imidization between monomers. The monomers required for the reaction are directly available commercially. Polyimide synthesis can be referred to: 10.1016/j.memsci.2018.08.031 (DOI).
Example 1
(1) 0.80g of 6FDA-DAM/DABA (3:2) polymer was weighed out and dissolved in 4.2g of CHCl3Stirring the solution for 1h, and completely dissolving 6FDA-DAM/DABA (3:2) to form a uniform polymer solution;
(2) 0.20gNi-gallate powder was dispersed in 9.8g of CHCl3In the solution, the solution is placed on a stirring table to be stirred for 3 hours after being subjected to ultrasonic treatment for 10 minutes.
(3) Mixing Ni-gate CHCl3The dispersion liquid is dropwise added into the polymer solution by a dropper, and the mixture is stirred for 48 hours in a fume hood to obtain a casting solution with uniform dispersion. Placing the scraper and glass plate with tin foil tape in the glove belt, inflating the glove belt with nitrogen gas, and making CHCl in the glove belt3An atmosphere. And (3) preparing a Ni-gate mixed matrix membrane on a glass plate by using a 100-micron scraper for the uniformly dispersed membrane casting solution, taking out the membrane after the organic solvent is completely volatilized, drying for 24 hours at room temperature, and aging for 24 hours in a vacuum drying oven at 120 ℃ to obtain the membrane with the thickness of about 15 microns, wherein the doping amount of Ni-gate in the mixed matrix membrane is 20%, and the error is within +/-1%.
(4) The film is subjected to single-component performance test under the conditions of 0.15MPa and 25 ℃, and the result shows that C is2H4Has a permeability of 10.40Barrer, C2H4/C2H6The selectivity was 4.18.
Comparative example 1: 1g of 6FDA-DAM/DABA (3:2) polymer was weighed out and dissolved in 4g of CHCl3Stirring the solution for 10min, and completely dissolving 6FDA-DAM/DABA (3:2) to form a uniform polymer solution; and then stirring the mixture in a fume hood for 48 hours to obtain the uniformly dispersed casting solution. Coating the casting solution in CHCl3Scraping the film in the glove belt of the atmosphere until CHCl is reached3Taking out the mixed matrix membrane after complete volatilization and solidification to form a membrane, drying the mixed matrix membrane for 12 hours at room temperature, then aging the mixed matrix membrane for 24 hours in a vacuum drying oven at 120 ℃, taking out the mixed matrix membrane, and carrying out single-component performance test under the conditions of 0.15MPa and 25 ℃, wherein the result shows that C2H4Has a permeability of 6.98Barrer, C2H4/C2H6The selectivity was 3.90. From a comparison of example 1 and comparative example 1, it can be seen that the Ni-gate/6 FDA-DAM/DABA (3:2) mixed matrix membrane is at C compared to the pure 6FDA-DAM/DABA (3:2) polymer membrane2H4Permeability and C of2H4/C2H6The selectivity is improved.
Example 2
(1) 0.05g, 0.10g, 0.20g, 0.30g and 0.5g of Ni-gate powder are weighed into 6 different 20ml glass bottles and marked a1, a2 to a5, and 9g of CHCl are added to each of the three bottles3And ultrasonically treating for 5min, and stirring for 1h on a stirring table. The corresponding 0.95g, 0.9g, 0.80g, 0.70g and 0.50g of 6FDA-DAM polymer were placed in glass bottles b1, b2 to b5, respectively, and 5g of CHCl were added3And placing on a turntable to stir for 1 h.
(2) Dropwise adding a1 into b1, dropwise adding a2 into b2 and dropwise adding b5 into a5 to prepare casting solution c1, c2 and c5 with the Ni-gate doping amounts of 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.% and 50 wt.%. And (3) placing the casting solution on a digital display roller blending instrument for mixing for 48 hours.
(3) In CHCl3And preparing a mixed matrix membrane by using a 300-micron scraper in the atmosphere, taking out the membrane after the solvent in the mixed matrix membrane is completely volatilized and the membrane is solidified, drying the membrane at room temperature for 12 hours, and drying the membrane in a vacuum drying oven at 120 ℃ for 24 hours to finally obtain the mixed matrix membrane with the thickness of about 50 microns. FIG. 1 is an electron microscope cross-sectional view of a 6FDA-DAM pure polymer film and a 20% Ni-gate/6 FDA-DAM mixed matrix film, showing that the Ni-gate particles are uniformly dispersed in the polymer and no significant defects are observed at the interface between the two.
(4) The preparation method of the mixed matrix film with different doping amounts c 2-c 5 is completely consistent with the step (3). Through thermogravimetric test, the doping amount error of each film is within +/-1%.
(5) The Ni-gate/6 FDA-DAM mixed matrix membrane with different doping amounts is tested under the conditions of 0.35Mpa and 35 ℃, and the properties are listed as follows:
| 5wt.％ | 10wt.％ | 20wt.％ | 30wt.％ | 50wt.％ | |
| ethylene Permeability (Barrer) | 64.96 | 71.52 | 86.80 | 105.87 | 92.86 |
| Ethylene/ethane selectivity | 2.83 | 3.00 | 3.36 | 3.77 | 3.87 |
Example 3
(1) Head0.80g of 6FDA-Durene powder is first weighed out and dissolved in 7.2g of CH2Cl2Stirring the solution for 1 hour to obtain a uniform polymer solution; 0.20g of Mg-gate powder was dispersed in 9.8gCH2Cl2In the solution, ultrasonic treatment is carried out for 10min, and then the solution is placed on a stirring table to be stirred for 1 h.
(2) Mixing Mg-gate CH2Cl2The dispersion liquid is dropwise added into the polymer solution by a dropper, and the mixture is stirred for 48 hours in a fume hood to obtain a casting solution with uniform dispersion. The Mg-gate/6 FDA-Durene mixed matrix membrane is prepared by blade coating on a glass plate, and the membrane is taken out after the solvent is completely volatilized. . Through thermogravimetric test, the doping amount error of each film is within +/-1%.
(3) The mixed matrix membrane was dried at room temperature for 12 hours and then aged in a vacuum oven at 120 ℃ for 24 hours to a membrane thickness of about 70 μm. Taking out the product, performing single-component performance test at 25 ℃ under 0.15MPa, and displaying test results to C2H4Has a permeability of 105.28Barrer, C2H4/C2H6The selectivity was 3.40.
(4) Weighing 1g of 6FDA-Durene powder, dissolving the powder in 4g of chloroform solution, stirring for 1h to obtain a uniform polymer solution, and then stirring for 48h to obtain a membrane casting solution. The 6FDA-Durene film is obtained by scraping and dried for 12h at room temperature and then aged for 24h in a vacuum oven at 120 ℃ to a film thickness of about 70 μm. After being taken out, the single component performance test is carried out at 25 ℃ under 0.15MPa, and the result shows that C2H4Has a permeability of 78.10Barrer, C2H4/C2H6The selectivity was 2.79.
(5) Mg-gallate/6FDA-Durene Mixed matrix membranes compared to pure Polymer membranes, C2H4The permeability of the steel is improved by 34.8 percent, C2H4/C2H6The selectivity is improved by 21.9 percent.
Example 4
(1) 0.80g of 6FDA-DAM powder was first weighed out and dissolved in 4gCH2Cl2Stirring the solution for 1 hour to obtain a uniform polymer solution; 0.20g of Ni-gate powder was dispersed in 9.8gCH2Cl2In the solution, ultrasonic treatment is carried out for 10min, and then the solution is placed on a stirring table to be stirredStirring for 1 h.
(2) Mixing Ni-galateCH2Cl2The dispersion liquid is dropwise added into the polymer solution by a dropper, and the mixture is stirred for 48 hours in a fume hood to obtain a casting solution with uniform dispersion. Coating the casting solution on CH2Cl2Scraping the film in the glove belt in the atmosphere, standing for 6h to wait for CH2Cl2And taking out the mixed matrix membrane after complete volatilization and solidification to form a membrane. The doping amount error of the mixed matrix membrane is within +/-1%.
(3) The mixed matrix membrane was dried at room temperature for 12 hours, and then aged in a vacuum oven at 120 ℃ for 24 hours to a mixed matrix membrane thickness of 57 μm. Taking out, and mixing at 25 deg.C2H4/C2H61:1 (volume ratio)) performance was tested as a function of operating pressure. Corresponding to C2H4Permeability and C2H4/C2H6The selectivity was as follows: 0.1 MPa: 89.60Barrer, 2.50; 0.2 Mpa: 87.34Barrer, 2.57; ③ 0.4 MPa: 86.70Barrer, 2.51; 0.6 Mpa: 85.79Barrer, 2.53; 0.8 Mpa: 83.69Barrer, 2.46; sixthly, 1 Mpa: 84.37Barrer, 2.37; seventhly, 1.5 Mpa: 96.54Barrer, 2.32; (viii) 2 Mpa: 104.75Barrer, 2.28.
(4) 1g of 6FDA-DAM powder was weighed out and dissolved in 4gCH2Cl2Stirring the solution for 1 hour to obtain a uniform membrane casting solution. Coating the casting solution on CH2Cl2Scraping the film in the glove belt in the atmosphere, standing for 6h to wait for CH2Cl2And taking out the pure 6FDA-DAM film after complete volatilization and solidification to form a film. The film was dried at room temperature for 12 hours and then aged in a vacuum oven at 120 ℃ for 24 hours to a film thickness of 61 μm. Taking out, and mixing at 25 deg.C2H4/C2H61:1 (volume ratio)) performance was tested as a function of operating pressure. Corresponding to C2H4Permeability and C2H4/C2H6The selectivity was as follows: 0.1 MPa: 78.63Barrer, 1.85; 0.2 Mpa: 77.34Barrer, 1.74; ③ 0.4 MPa: 72.70Barrer, 1.61; 0.6 Mpa: 70.53Barrer, 1.53; 0.8 Mpa: 68.39Barrer, 1.46; sixthly, 1 Mpa: 75.07Barrer, 1.37; seventhly, 1.5 Mpa: 86.54Barrer, 1.32; (viii) 2 Mpa: 94.32Barrer, 1.28.
(5)20 wt.% Ni-gate/6 FDA-DAM mixed matrix membrane compared to pure 6FDA-DAM membrane C in the stress test range2H4Permeability and C2H4/C2H6The selectivity is comprehensively superior to that of a pure 6FDA-DAM membrane.
Example 5
(1) Weighing 0.9g of 6FDA-DAM powder, dissolving in 4.1g of THF solution, and stirring for 10min to obtain a uniform polymer solution; 0.10g of Co-gate powder was dispersed in 4.9g of THF solution, sonicated for 10min and then placed on a stirring table and stirred for 1 h.
(2) And dropwise adding the Co-gate THF dispersion into a 6FDA-DAM THF solution by using a dropper, and dispersing for 48 hours on a digital roller mixer to obtain a uniform casting solution. And (3) scraping the membrane casting solution in a glove belt in a THF atmosphere, standing for 6h, and taking out the mixed matrix membrane after the THF is completely volatilized and solidified to form a membrane. The doping amount error is within +/-1% through thermogravimetric test.
(3) The mixed matrix membrane was dried at room temperature for 12 hours, and then aged in a vacuum oven at 120 ℃ for 24 hours to have a membrane thickness of 42 μm. After being taken out, the material is subjected to long-term stability test at 25 ℃ and 0.15 MPa. As shown in FIG. 2, Co-gate/6 FDA-DAM mixed matrix membranes tested for up to 120h, C2H4Permeability of about 70Barrer and slightly decreased, C2H4/C2H6The selectivity was 2.56 and increased with increasing test time, with good membrane stability.
Example 6
(1) Weighing 0.90g of Matrimid powder, dissolving the Matrimid powder in 8.1g of THF solution, and stirring for 30min to obtain uniform Matrimid solution; 0.10g of Co-gate powder was dispersed in 9.9g of THF solution, sonicated for 10min and then placed on a stirring table and stirred for 1 h.
(2) Dropwise adding the Ni-gate THF dispersion liquid into the Matrimide solution by using a dropper, and dispersing for 48 hours on a digital display roller mixing machine in a fume hood to obtain a uniform casting film liquid. And (3) scraping the membrane casting solution in a glove belt in a THF atmosphere, standing for 6h, and taking out the mixed matrix membrane after the THF is completely volatilized and solidified to form a membrane.
(3) Drying the mixed matrix membrane at room temperature for 12h, aging in a vacuum drying oven at 120 deg.C for 24h to obtain a membrane with a thicknessIt was 63 μm. After being taken out, the alloy is subjected to performance test at 0.35MPa and 35 ℃, and the result shows that C is2H4Has a permeability of 0.61Barrer, C2H4/C2H6The selectivity was 4.91. Compared with a pure Matrimid membrane, the permeability is improved by 35.56 percent, and the content of C is increased2H4/C2H6The selectivity is improved by 9.11 percent.
Claims (7)
1. A metal organic framework M-gate mixed matrix membrane is characterized in that: the M-gate mixed matrix membrane is formed by mixing M-gate particles and a polyimide polymer; wherein the mass of the M-gap particles accounts for 5-50% of the total mass of the M-gap particles and the polyimide.
2. The metal-organic framework M-gate mixed matrix membrane according to claim 1, wherein: the M-gate is Mg-gate, Ni-gate or Co-gate.
3. The metal-organic framework M-gate mixed matrix membrane according to claim 1, wherein: the polyimide polymer is a polyimide material synthesized by matrix or dianhydride monomer containing trifluoromethyl; wherein the polyimide material synthesized by the dianhydride monomer containing trifluoromethyl is 6FDA-DAM, 6FDA-Durene, 6FDA-DAM/DABA or 6 FDA-NDA/Durene.
4. The metal-organic framework M-gate mixed matrix membrane according to claim 1, wherein: the thickness of the mixed matrix film is 10-75 μm.
5. A method for preparing the metal-organic framework M-gate mixed matrix membrane according to claim 1, which comprises the following specific steps:
a) weighing a polyimide polymer, mixing and stirring the polyimide polymer with an organic solvent to obtain a polyimide solution with the mass concentration of 7-20%;
b) weighing M-gate particles, adding the M-gate particles into an organic solvent, performing ultrasonic treatment, mixing and stirring to obtain M-gate dispersion liquid with the mass concentration of 0.5-6%;
c) respectively taking M-gate dispersion liquid and polyimide solution according to the mass of the M-gate particles accounting for 5% -50% of the total mass of the M-gate particles and the polyimide, and mixing and stirring to obtain uniformly dispersed membrane casting liquid;
d) a self-supporting M-gate mixed matrix membrane was obtained by means of knife coating.
6. The method of claim 5, wherein: the organic solvent in the steps a) and b) is trichloromethane, dichloromethane or tetrahydrofuran.
7. Use of a metal organic framework M-gate mixed matrix membrane according to claim 1 for ethylene/ethane gas separation.
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