CN114100380A - Mixed matrix membrane with through channel structure and preparation and application thereof - Google Patents
Mixed matrix membrane with through channel structure and preparation and application thereof Download PDFInfo
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- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title description 11
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 68
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000012528 membrane Substances 0.000 claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 8
- 230000005484 gravity Effects 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 238000000935 solvent evaporation Methods 0.000 claims abstract description 7
- 239000002356 single layer Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- 238000005266 casting Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 11
- 239000005357 flat glass Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 28
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 26
- 238000000926 separation method Methods 0.000 abstract description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001294 propane Substances 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012917 MOF crystal Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000012920 MOF membrane Substances 0.000 description 1
- -1 ZIF-67 Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000010129 solution processing Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a mixed matrix membrane with a through channel structure, which comprises a polymer matrix and a porous filler, wherein the polymer matrix is 6FDA-DAM, the porous filler is a metal organic framework material ZIF-8, and the mass ratio of the ZIF-8 to the 6FDA-DAM is 11.1-66.7: 100; in the mixed matrix membrane, an embedded single-layer ZIF-8 crystal penetrates through the 6FDA-DAM to form an efficient and firm gas through channel. The mixed matrix membrane is mainly prepared by three steps of preparing 6FDA-DAM, synthesizing ZIF-8 with the crystal granularity of 4-6 mu m and adopting solvent evaporation/gravity cooperative driving self-assembly membrane forming; the prepared mixed matrix membrane is used for a propylene/propane gas separation system, has high flux and high selectivity on propylene, and has excellent pressure resistance, good mechanical property and operation stability.
Description
Technical Field
The invention relates to a preparation method of a mixed matrix membrane with a ZIF-8 straight-through channel and application of the mixed matrix membrane in propylene-propane separation, belonging to the technical field of gas separation membranes and mixed matrix membranes.
Background
Olefins are one of the largest organic chemicals produced worldwide, with yields exceeding 2 million tons, for the production of polyolefins, ethylene oxide, and the like. The ethylene yield is also an important mark for measuring the development level of the chemical industry in China. At present, a certain amount of alkane is often accompanied in olefin production, and rectification technology is the mainstream technology of olefin/alkane separation at present. However, because the difference between the boiling points of the two components is small, the energy consumption of the rectification method is extremely high, and the energy consumption accounts for about 0.3 percent of the total global energy consumption, the development of an efficient olefin and alkane separation technology has important significance for the sustainable development of modern chemical industry. Non-thermal based gas separation membrane technologies are expected to play an important role in this field and to reduce the energy consumption of the separation process substantially. It is estimated that if membrane technology is used instead of energy intensive distillation technology to achieve this separation, more than 80% of the energy can be saved and in order to achieve the application of membrane technology, membrane materials must be developed that can effectively separate propylene and propane.
Metal Organic Frameworks (MOFs), represented by ZIF series materials, are considered to be one of the most promising propylene/propane separation membrane materials due to their highly tunable structures and excellent molecular sieving capabilities. Wherein the star material ZIF-8 has an effective window size of
Between C3H6And C3H8The molecular size is between, and the molecular sieving performance is obvious. However, the use efficiency of polycrystalline ZIF-8 films is severely limited due to poor film forming properties and poor pressure stability.
Mixed matrix membranes, which combine the molecular sieving capabilities of porous crystals with the solution processing capabilities of polymers, are considered a viable solution. Currently, most mixed matrix membranes are prepared by dispersing MOF porous crystals in a polymer matrix. The size of the MOF crystals is much smaller than the thickness of the film. This membrane structure provides a convenient solution for improving the separation performance of polymers, and in particular overcomes the trade-off between permeability and selectivity of polymer membranes. However, the separation performance of these mixed matrix membranes tends to be significantly lower than that of pure MOF membranes, because the MOF crystals are mostly encapsulated by the polymeric matrix, which serves as the main molecular transport channel. Therefore, the mixed matrix membrane is expected to be further developed in the field of propylene/propane separation by fully utilizing the molecular sieving performance of the MOF material.
Disclosure of Invention
Aiming at the prior art, the invention provides a mixed matrix membrane with an MOF-based through channel, a preparation method and application thereof, the preparation method is simple, convenient and controllable, and the prepared homogeneous membrane can be used for C3H6/C3H8The system gas separation process has high separation performance and pressure stability.
In order to solve the technical problems, the mixed matrix membrane with the through channel structure comprises a polymer matrix and a porous filler, wherein the polymer matrix is 6FDA-DAM, the porous filler is a metal organic framework material ZIF-8, and the mass ratio of the metal organic framework material ZIF-8 to the 6FDA-DAM is 11.1-66.7: 100; the mixed matrix membrane is prepared by a solvent evaporation/gravity cooperative driving self-assembly method, and an embedded single-layer metal organic framework material ZIF-8 crystal penetrates through the 6FDA-DAM to form an efficient and firm gas through channel, so that the mixed matrix membrane with the thickness of 4-6 mu m and a through channel structure is prepared.
The preparation method of the mixed matrix membrane with the through channel structure comprises the following steps:
1) taking 6FDA and DAM as monomers to carry out imidization polycondensation reaction to prepare 6 FDA-DAM;
2) preparing a metal organic framework material ZIF-8 with the crystal size of 4-6 mu m by taking zinc nitrate and 2-methylimidazole as monomers;
3) the mixed matrix membrane is prepared by a self-assembly method driven by solvent evaporation/gravity.
Further, the operation process of step 3) is as follows:
3-1) dissolving a proper amount of 6FDA-DAM in an anhydrous DMF solvent to prepare a PI solution with the mass percent of 0.4%, stirring at room temperature for 12h, and filtering by a 0.8 mu m needle type organic filter head to obtain a 6FDA-DAM transparent solution;
3-2) dispersing a metal organic framework material ZIF-8 in an anhydrous DMF solvent to prepare a stable ZIF-8 suspension;
3-3) adding a certain amount of ZIF-8 suspension into a 6FDA-DAM transparent solution, wherein the mass ratio of the ZIF-8 to the 6FDA-DAM is 11.1-66.7: 100; ultrasonically dispersing for at least 1h to obtain 6FDA-DAM dispersion liquid of ZIF-8; supplementing anhydrous DMF solvent to enable the mass concentration of the ZIF-8 dispersion to be 0.1-0.4 wt%, and continuously stirring for more than 12h to obtain a membrane casting solution;
3-4) performing ultrasonic and static defoaming treatment on the casting solution, slowly coating the casting solution on a wetted super-flat glass surface dish, and placing the dish in a constant-temperature drying oven at 80 ℃ in a DMF (dimethyl formamide) steam atmosphere; placing the tinfoil with holes on an ultra-flat glass surface dish to control the film forming time to be 70-74 h;
3-5) naturally cooling to room temperature after film formation, and pouring a small amount of deionized water into the watch glass to enable the film to naturally fall off from the surface of the super-flat glass watch glass; the film was placed in a vacuum oven for vacuum drying at 210 ℃ for 24h for heat treatment to remove residual solvent and ensure complete imidization of the polyimide.
The ZIF-8 through channel mixed matrix membrane prepared by the preparation method is used for C3H6/C3H8System C3H6Separating, at 30 deg.C and 1bar pressure of raw material gas, C3H6485-3H6/C3H8The selectivity is 35.6-42.8; under the condition of 30 ℃ and 5bar of raw gas pressure, C3H6Flux maintenance at 322-489Barrer, C3H6/C3H8The selectivity is maintained between 33.6 and 38.9.
The invention has the advantages that: the membrane material has the advantages of simple preparation process, high controllability, easily obtained raw materials and strong universality. The prepared homogeneous film shouldFor C3H6/C3H8Separation system, pair C3H6Has high permeation flux and high selectivity, and the mixed matrix membrane has good mechanical property and time stability.
Drawings
FIG. 1 is a surface electron micrograph of a film 1 obtained in example 1;
FIG. 2 is a surface electron micrograph of the film 2 obtained in example 2;
FIG. 3 is a surface electron micrograph of the film 3 obtained in example 3;
FIG. 4 is a surface electron micrograph of the film 4 obtained in example 4;
FIG. 5 is C of the films obtained in examples 1 to 6 and the films obtained in comparative examples 1 and 23H6Permeate flux and C3H6/C3H8Selectivity performance versus plot.
Detailed Description
The mixed matrix membrane with the MOF-based through channel structure comprises a polymer matrix and a porous filler, wherein the polymer matrix is 6FDA-DAM, the porous filler is a metal organic framework material ZIF-8, and the mass ratio of the metal organic framework material ZIF-8 to the 6FDA-DAM is 11.1-66.7: 100; in the mixed matrix membrane, an embedded single-layer metal organic framework material ZIF-8 crystal penetrates through the 6FDA-DAM to form an efficient and firm gas through channel. The mixed matrix membrane is mainly prepared by three steps of preparing polyimide polymer (6FDA-DAM), synthesizing a metal organic framework material ZIF-8 and adopting solvent evaporation/gravity cooperative driving self-assembly membrane forming; wherein, the synthesized ZIF-8 crystal particle size is 4-6 μm, the ZIF-8 mass fraction in the prepared mixed matrix membrane is 10-40 wt%, and the membrane thickness is 4-6 μm. The mixed matrix membrane prepared by the invention is used for a propylene/propane gas separation system, has high flux and high selectivity on propylene, and has excellent pressure resistance, good mechanical property and operation stability.
The technical solution of the present invention is further described in detail with reference to the following specific embodiments and the attached table, and the described specific embodiments are only illustrative of the present invention and are not intended to limit the present invention.
Example 1:
preparing a mixed matrix membrane with a ZIF-8-based through channel, comprising the following steps of:
step 1) taking 6FDA and DAM as monomers to perform imidization and polycondensation reaction to prepare 6 FDA-DAM:
the purified 6FDA and DAM were dried in a vacuum oven at 100 ℃ and 40 ℃ for more than 24h, respectively. A monomer solution was prepared stoichiometrically by adding 10mmol of 6FDA and 10mmol of DAM to 100mL bottles, respectively, and DMAc was 25.5 mL. The proportion of monomers in the solution was 20%. The reaction mixture was stirred with a mechanical stirrer at 0 ℃ under a nitrogen purge atmosphere for 24 hours, and then imidized by adding acetic anhydride (dehydrating agent) and triethylamine (catalyst) under a nitrogen purge at room temperature for 24 hours. Precipitating the polymer solution by using methanol, washing the polymer solution by using cold methanol for three times, and drying the polymer solution for 24 hours in a vacuum oven at the temperature of 200 ℃ to obtain the polyimide polymer 6 FDA-DAM.
Step 2) preparing a metal organic framework material ZIF-8 with the crystal size of 4-6 mu m by taking zinc nitrate and 2-methylimidazole as monomers:
734.4mg Zn (NO)3)2·6H2O was dissolved in 100ml of methanol to obtain a first solution. A second solution was prepared by dissolving 810.6mg of 2-methylimidazole and 810.6mg of 1-methylimidazole in 100ml of methanol. The second solution was poured into the first solution with stirring using a magnetic bar. Stirring is stopped after 5 min. The reaction was carried out at 0 ℃ for 36h to give the product as a white solid. The product is washed by centrifugation (8000rpm,5 minutes), and is subjected to two times of dispersion/centrifugation circulation by taking methanol as a solvent, so as to obtain the metal organic framework material ZIF-8 with the crystal grain size of 4-6 mu m.
Step 3) preparing the mixed matrix membrane by a solvent evaporation/gravity cooperative driving self-assembly method: the specific process is as follows:
3-1) dissolving a proper amount of 6FDA-DAM in an anhydrous DMF solvent to prepare a PI solution with the mass percent of 0.4%, stirring at room temperature for 12h, and filtering by a 0.8 mu m needle type organic filter head to obtain a 6FDA-DAM transparent solution;
3-2) dispersing a metal organic framework material ZIF-8 in an anhydrous DMF solvent to prepare a stable ZIF-8 suspension;
3-3) adding a certain amount of ZIF-8 suspension into 10g of 6FDA-DAM transparent solution, wherein the mass ratio of the ZIF-8 to the 6FDA-DAM is 11.1%; ultrasonically dispersing for 1h to obtain 6FDA-DAM dispersion liquid of ZIF-8; supplementing anhydrous DMF solvent to make the total volume of the membrane casting solution be 20ml (namely the mass fraction of ZIF-8 in the dispersion is 0.1wt percent), and continuously stirring for 12h to prepare the membrane casting solution;
3-4) before membrane pouring, carrying out ultrasonic and static defoaming treatment on the membrane casting solution, then slowly coating the membrane casting solution on a wetted super-flat glass surface dish, placing the dish in a constant-temperature drying box at 80 ℃ in a DMF (dimethyl formamide) steam atmosphere, placing the tinfoil with holes on the super-flat glass surface dish, and controlling the evaporation rate of the solvent by using the number of the open holes of the tinfoil to ensure that the membrane forming time is about 72 hours.
3-5) naturally cooling to room temperature after film formation, pouring a small amount of deionized water into the watch glass, and soaking for a while to ensure that the film naturally falls off from the surface of the super-flat glass watch glass; and (3) placing the obtained film in a vacuum oven for vacuum drying at 210 ℃ for 24h for heat treatment, removing residual solvent and ensuring that the polyimide is completely imidized, and marking the finally obtained mixed matrix film as a film 1, wherein the surface electron microscope image of the film 1 is shown in FIG. 1.
The membrane 1 is used in a propylene/propane separation system, under the conditions of 30 ℃ and 1bar of raw material gas pressure, C3H6Flux of 386Barrer, C3H6/C3H8The selectivity was 28.6 as shown in FIG. 5.
Example 2:
a mixed matrix membrane having a ZIF-8-based through channel was prepared, and example 2 was prepared substantially in the same manner as example 1, except that: in the step 3-3), the mass ratio of the metal organic framework material ZIF-8 to 6FDA-DAM is changed to 25% from 11.1%, an anhydrous DMF solvent is supplemented, so that the mass fraction of ZIF-8 in the membrane casting solution is 0.1 wt%, and the finally obtained mixed matrix membrane is marked as a membrane 2. Fig. 2 shows a surface electron micrograph of the film 2.
The membrane 2 is used in a propylene/propane separation system, and the pressure of the raw material gas is 1bar at the temperature of 30 DEG C3H6Flux of 408Barrer, C3H6/C3H8SelectingThe sex was 29.1 as shown in fig. 5.
Example 3:
a mixed matrix membrane having a ZIF-8-based through channel was prepared, and example 2 was prepared substantially in the same manner as example 1, except that: in the step 3-3), the mass ratio of the ZIF-8 to the 6FDA-DAM is changed to 42.8% from 11.1%, and an anhydrous DMF solvent is supplemented to ensure that the mass fraction of the ZIF-8 in the casting solution is 0.1 wt%, and finally the obtained mixed matrix membrane is marked as a membrane 3. Fig. 3 shows a surface electron micrograph of the film 3.
The membrane 3 is used in a propylene/propane separation system, under the conditions of 30 ℃ and 1bar of raw material gas pressure, C3H6Flux 510Barrer, C3H6/C3H8The selectivity was 38.8 as shown in FIG. 5.
Example 4:
a mixed matrix membrane having a ZIF-8-based through channel was prepared, and example 2 was prepared substantially in the same manner as example 1, except that: in the step 3-3), the mass ratio of the metal organic framework material ZIF-8 to 6FDA-DAM is changed to 66.8% from 11.1%, an anhydrous DMF solvent is supplemented, so that the mass fraction of the ZIF-8 in the casting solution is 0.1 wt%, and the finally obtained mixed matrix membrane is marked as a membrane 4. Fig. 4 shows a surface electron micrograph of the film 4.
The membrane 4 is used in a propylene/propane separation system, under the conditions of 30 ℃ and 1bar of raw gas pressure C3H6A flux of 582Barrer, C3H6/C3H8The selectivity was 42.8 as shown in FIG. 5.
Example 5:
a mixed matrix membrane having a ZIF-8-based through channel was prepared, and example 2 was prepared substantially in the same manner as example 1, except that: in the step 3-3), the mass ratio of the metal organic framework material ZIF-8 to 6FDA-DAM is 66.8%, an anhydrous DMF solvent is supplemented, so that the mass fraction of ZIF-8 in the membrane casting solution is changed to 0.2 wt%, and the finally obtained mixed matrix membrane is marked as membrane 5.
The membrane 5 is used in a propylene/propane separation system, under the conditions of 30 ℃ and 1bar of raw gas pressure, C3H6Flux 585Barrer, C3H6/C3H8The selectivity was 41.6 as shown in FIG. 5.
Example 6:
a mixed matrix membrane having a ZIF-8-based through channel was prepared, and example 2 was prepared substantially in the same manner as example 1, except that: in the step 3-3), the mass ratio of the metal organic framework material ZIF-8 to 6FDA-DAM is 66.8%, an anhydrous DMF solvent is supplemented, so that the mass fraction of ZIF-8 in the membrane casting solution is changed to 0.4 wt%, and the finally obtained mixed matrix membrane is marked as a membrane 6.
The membrane 6 is used in a propylene/propane separation system, under the conditions of 30 ℃ and 1bar of raw gas pressure, C3H6Flux 545Barrer, C3H6/C3H8The selectivity was 42.4 as shown in FIG. 5.
Comparative example 1:
a pure 6FDA-DAM membrane was prepared by the following steps:
0.04g of the polyimide polymer 6FDA-DAM prepared according to the step 1) of the example 1 is dissolved in an anhydrous DMF solvent to prepare a PI solution with the mass percent of 0.4 percent, the PI solution is stirred for 12 hours at room temperature and filtered by a needle type organic filter head with the diameter of 0.8 mu m to obtain a transparent solution of the 6FDA-DAM, and the stirring is continued for more than 12 hours. Before membrane pouring, the membrane casting solution is subjected to ultrasonic treatment and static defoaming treatment, and then the membrane casting solution is poured onto a super-flat glass surface dish and placed in a constant temperature drying oven at 80 ℃ in a DMF steam atmosphere. The tinfoil with holes is placed on a watch glass, and the evaporation rate of the solvent is controlled by the number of the open pores of the tinfoil, so that the film forming time is about 72 hours. After film formation, the glass plate is naturally cooled to room temperature, a small amount of deionized water is poured into the glass plate, and the glass plate is soaked for a while to enable the film to naturally fall off from the surface of the glass plate. The prepared membrane was placed in a vacuum oven for vacuum drying at 210 ℃ for 24h for heat treatment, and the obtained pure 6FDA-DAM membrane was designated as comparative example 1.
The membrane of comparative example 1 was used in a propylene/propane separation system at 30 ℃ and a feed gas pressure of 1bar C3H6Flux of 25Barrer, C3H6/C3H8The selectivity was 7.9 as shown in FIG. 5.
Comparative example 2:
the preparation method of the mixed matrix composite membrane with the ZIF-8-based through channel comprises the following steps:
the preparation process of the composite membrane with the mixed matrix of the ZIF-8-based through channel is basically the same as that of the example 1, except that: in steps 3-3 and 3-4), the mass ratio of the metal organic framework material ZIF-8 to 6FDA-DAM is changed to 40% from 11.1%, an anhydrous DMF solvent is supplemented, the mass fraction of ZIF-8 in the casting solution is 0.1 wt%, the casting solution is slowly coated on a wetted polyacrylonitrile filter membrane, and the obtained mixed matrix membrane is marked as comparative example 2.
The membrane 2 is used in a propylene/propane separation system, and the pressure of the raw material gas is 1bar at the temperature of 30 DEG C3H6Flux is 122GPU, C3H6/C3H8The selectivity was 24.6 as shown in FIG. 5.
According to the preparation method, the mass ratio of the ZIF-8 to the 6FDA-DAM is regulated to 11.1-66.7: 100, the ZIF-8 crystal granularity can be controlled, so that the thickness of the through mixed matrix membrane is controlled, the thickness of the through mixed matrix membrane is reduced by applying the ZIF-8 with the small particle size, the mass transfer resistance of the membrane is reduced, and the permeation flux of the mixed matrix membrane is improved. Compared with a pure 6FDA-DAM membrane, the ZIF-8 molecular sieving channel is introduced, and compared with a non-penetrating mixed matrix membrane, the penetrating structure maximizes the molecular sieving performance and simultaneously improves the membrane selectivity and the permeation flux. As can be seen from SEM images of the membrane surfaces of FIGS. 1 to 4, the surface of the ZIF-8 crystal is exposed on the membrane surface, and the embedded single-layer metal organic framework material ZIF-8 crystal penetrates through the 6FDA-DAM to form a high-efficiency and firm molecular sieving through channel.
Although the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, which are only illustrative and not restrictive, and those skilled in the art can make many modifications without departing from the spirit of the present invention, and it is within the scope of the present invention to use other metal organic framework materials such as ZIF-67, MOF-based through channel structure composite membranes prepared from polymer substrates (comparative example 2), and mixed matrix membranes prepared from the present invention for other gas separation fields.
Claims (4)
1. The mixed matrix membrane with the through channel structure is characterized by comprising a polymer matrix and a porous filler, wherein the polymer matrix is 6FDA-DAM, the porous filler is a metal organic framework material ZIF-8, and the mass ratio of the metal organic framework material ZIF-8 to the 6FDA-DAM is 11.1-66.7: 100; the mixed matrix membrane is prepared by a solvent evaporation/gravity cooperative driving self-assembly method, and an embedded single-layer metal organic framework material ZIF-8 crystal penetrates through the 6FDA-DAM to form an efficient and firm gas through channel, so that the mixed matrix membrane with the thickness of 4-6 mu m and a through channel structure is prepared.
2. A method for producing a mixed matrix membrane having a through-channel structure according to claim 1, comprising the steps of:
1) taking 6FDA and DAM as monomers to carry out imidization polycondensation reaction to prepare 6 FDA-DAM;
2) preparing a metal organic framework material ZIF-8 with the crystal size of 4-6 mu m by taking zinc nitrate and 2-methylimidazole as monomers;
3) the mixed matrix membrane is prepared by a self-assembly method driven by solvent evaporation/gravity.
3. The method for producing a mixed matrix membrane according to claim 2, wherein step 3) includes:
3-1) dissolving a proper amount of 6FDA-DAM in an anhydrous DMF solvent to prepare a PI solution with the mass percent of 0.4%, stirring at room temperature for 12h, and filtering by a 0.8 mu m needle type organic filter head to obtain a 6FDA-DAM transparent solution;
3-2) dispersing a metal organic framework material ZIF-8 in an anhydrous DMF solvent to prepare a stable ZIF-8 suspension;
3-3) adding a certain amount of ZIF-8 suspension into a 6FDA-DAM transparent solution, wherein the mass ratio of the ZIF-8 to the 6FDA-DAM is 11.1-66.7: 100; ultrasonically dispersing for at least 1h to obtain 6FDA-DAM dispersion liquid of ZIF-8; supplementing a proper amount of anhydrous DMF solvent to ensure that the mass concentration of the ZIF-8 dispersion liquid is 0.1-0.4 wt%, and continuously stirring for more than 12h to prepare a membrane casting liquid;
3-4) performing ultrasonic and static defoaming treatment on the casting solution, slowly coating the casting solution on a wetted super-flat glass surface dish, and placing the dish in a constant-temperature drying oven at 80 ℃ in a DMF (dimethyl formamide) steam atmosphere; placing the tinfoil with holes on an ultra-flat glass surface dish to control the film forming time to be 70-74 h;
3-5) naturally cooling to room temperature after film formation, and pouring a small amount of deionized water into the watch glass to enable the film to naturally fall off from the surface of the super-flat glass watch glass; the film was placed in a vacuum oven for vacuum drying at 210 ℃ for 24h for heat treatment to remove residual solvent and ensure complete imidization of the polyimide.
4. Use of the mixed matrix membrane having a through-channel structure according to claim 1 or the mixed matrix membrane having a through-channel structure obtained by the production method according to claim 2 or 3 for C3H6/C3H8System C3H6Separating, at 30 deg.C and 1bar pressure of raw material gas, C3H6485-3H6/C3H8The selectivity is 35.6-42.8; under the condition of 30 ℃ and 5bar of raw gas pressure, C3H6Flux maintenance at 322-489Barrer, C3H6/C3H8The selectivity is maintained between 33.6 and 38.9.
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| US20160263534A1 (en) * | 2015-03-11 | 2016-09-15 | The Board Of Regents Of The University Of Texas System | Compatibilized immiscible polymer blends and molecular sieve membranes thereof |
| CN112156661A (en) * | 2020-09-15 | 2021-01-01 | 南京工业大学 | Multilayer composite membrane for efficient separation of C3H6/C3H8 and preparation method thereof |
| CN112221362A (en) * | 2020-10-21 | 2021-01-15 | 天津大学 | Quaternized polysulfone homogeneous membrane with ion cluster structure, and preparation and application thereof |
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| US20160263534A1 (en) * | 2015-03-11 | 2016-09-15 | The Board Of Regents Of The University Of Texas System | Compatibilized immiscible polymer blends and molecular sieve membranes thereof |
| CN112156661A (en) * | 2020-09-15 | 2021-01-01 | 南京工业大学 | Multilayer composite membrane for efficient separation of C3H6/C3H8 and preparation method thereof |
| CN112221362A (en) * | 2020-10-21 | 2021-01-15 | 天津大学 | Quaternized polysulfone homogeneous membrane with ion cluster structure, and preparation and application thereof |
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