CN113713636A - Mixed matrix membrane based on PIM-1 and preparation method thereof - Google Patents
Mixed matrix membrane based on PIM-1 and preparation method thereof Download PDFInfo
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- 101001001642 Xenopus laevis Serine/threonine-protein kinase pim-3 Proteins 0.000 title claims abstract description 58
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Images
Classifications
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Abstract
The invention discloses a mixed matrix membrane based on PIM-1 and a preparation method thereof, belonging to the technical field of membrane materials. The preparation method takes a polymer PIM-1 with micropores as a membrane main body, takes metal-organic framework material MOF-808(Zr) as an additive, and is prepared by a solvent casting-evaporation method, and comprises the preparation steps of MOF-808(Zr), PIM-1 and MOF-808@ PIM-1 membrane. The comparative graph of the permeability of the invention shows that MOF-808@ PIM-1 mixed matrix membrane with different composition ratios is opposite to ethyl acetate/N2All have certain osmotic selectivity, when the amount of the MOF-808 doped is controlled in an optimal range, the permeation rate of ethyl acetate is increased, and the osmotic selectivity is increased. The invention can be used for treating waste gas containing VOCs.
Description
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a PIM-1-based mixed matrix membrane and a preparation method thereof.
Background
Ethyl acetate, as a common industrial solvent and an important organic synthetic raw material, is widely used. Ethyl acetate belongs to a low-toxicity chemical reagent, is volatile, stimulates sensitive parts of eyes, nose, throat and the like after a human body contacts the ethyl acetate, has acute toxic reaction symptoms of headache, dizziness, hypodynamia, chest distress, nausea, vomiting, abdominal pain and appetite reduction, can generate anesthetic action on the human body by inhaling high-concentration ethyl acetate steam, is easy to cause acute pulmonary edema and causes damage to the liver and the kidney in different degrees. The damage of ethyl acetate poisoning to human liver and cardiac muscle is long in duration and slow in recovery.
Polymers of Intrinsic Microporosity (PIMs) are a special class of polymeric materials with interconnected intermolecular voids, usually with high specific surface areas. Since the monomer structures constituting PIMs often have strong rigid "twisted sites" in their main chains themselves, resulting in inefficient close stacking of molecular chains, rather than a non-planar twisted spatial structure, such voids generated between polymer molecular chains are called free volume, and when the free volume is sufficiently large and integrally connected, a microporous structure having a pore diameter of less than 2 nm is generated. PIM-1 is a linear self-microporous polymer which is widely studied at present, and is prepared by using a monomer with a twisted helical structure: 5,5 ', 6,6 ' -tetrahydroxy-3, 3 ', 3,3 ' -tetramethyl-1, 1 ' -spirobiindane (TTSBI) and tetrafluoro monomers: tetrafluoroterephthalonitrile (TFTPN) is prepared by polycondensation reaction. PIM-1 has a large specific surface area (760-. It is worth mentioning that PIM-1 has excellent solvent resistance, which is currently known to be soluble only in chloroform, dichloromethane and tetrahydrofuran, and can maintain good stability even in most organic-aqueous solutions.
As a new nano porous material, a Metal-Organic Frameworks (MOFs) material is a coordination polymer formed by self-assembly reaction of Metal ions and Organic ligands, and has extremely important research value in the fields of gas adsorption, chemical catalysis, biomedicine, electrochemistry and the like. A secondary unit Structure (SBU) of the MOF-808(Zr) is a hexavalent zirconium metal cluster, is connected with trimesic acid serving as a ligand to form a super-tetrahedral stable structure, and is continuously extended through bridging with other organic ligands. Single crystal diffraction analysis showed that each sub-unit Structure (SBU) in the MOF-808 structure was linked to 6 different BTC 3-ligands and each BTC 3-ligand was linked to three different SBUs, resulting in complete coordination of the hexavalent zirconium clusters to the ligands due to charge balance. The coordination of the formate anion (-COO-) on the BTC 3-ligand to the Zr atom on the hexavalent zirconium cluster occurs in disorder in the form of monodentate and bidentate ligands. MOF-808 has a 6, 3-linked three-dimensional framework, as well as an overall spn topology, forming a tetrahedral cage with an internal pore diameter of 4.8 a, with SBU as the vertices of the tetrahedron and organic ligands BTC making up the four faces of the tetrahedron. Because each tetrahedral cage is connected with each other in a mode of sharing vertexes, the whole structure of the MOF-808 can be simplified into an infinitely extending rhombic net, and the connection of the small tetrahedral cages also forms a large cage with an inner hole diameter of 18.4A and a similar adamantane structure. The high coordination number of MOF-808 gives it excellent structural stability, while the two different sizes of pore-cage structures in the structure make MOF-808 exhibit very excellent performance in catalysis, gas adsorption and separation.
In conclusion, the mixed matrix membrane material which takes the polymer PIM-1 with micropores as a substrate and contains the stable and porous metal-organic framework MOF-808 has rich research significance and great application prospect in the field of membrane material application.
The information disclosed in this background is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
For the prior art, there has been a search, and chinese patent document CN112755801A discloses a preparation method of a mixed matrix membrane material, which is also a preparation method of a mixed matrix membrane material applied by the present applicant, and the mixed matrix membrane material is prepared by mixing MIL-101(Cr) as an organic particle additive with Pebax and an ethanol/water solvent, although CN112755801A has similarities with the preparation method, the detection method and the use of the membrane material of the present invention, CN112755801A is a different product from the present invention, and the used raw materials and products are different, and the intermediate products and intermediate steps are different, so that the present invention belongs to inventions of different inventive concepts.
Disclosure of Invention
In view of the above, to solve the above technical problems, the present invention is directed to a PIM-1-based device
The mixed matrix membrane and the preparation method thereof are used for preparing the mixed matrix membrane material which takes the polymer PIM-1 with micropores as a substrate and contains stable and porous metal-organic framework MOF-808.
The adopted technical scheme is as follows:
the preparation method of the mixed matrix membrane based on the PIM-1 comprises the following steps:
s1, preparing MOF-808(Zr) crystals:
s11, firstly, dissolving trimesic acid and zirconium oxychloride octahydrate in deionized water, adding acetic acid and concentrated hydrochloric acid, and sealing in a heating, condensing and refluxing device;
s12, placing the round-bottom flask which is heated in the condensation reflux device in the S11 into an oil bath for continuous reaction, slowly cooling to room temperature after the reaction is finished, and filtering and collecting a generated solid product;
s13, repeatedly washing and filtering the solid product obtained in the step S12 by using deionized water for several times, placing the solid product into a glass bottle, adding the deionized water, stirring, standing, repeating the process for several times, repeatedly washing and filtering by using ethanol for several times, and filtering to collect a generated precipitate product;
s14, placing the precipitation product obtained in the step S13 in a blast drying oven for drying, and obtaining MOF-808(Zr) crystals;
s2, PIM-1 preparation:
s21, weighing TTSBI, placing the TTSBI in a flat-bottom beaker, adding anhydrous methanol, stirring at a constant speed until the solid is completely dissolved, placing the beaker on a heating plate, continuously heating until the solution is boiled, filtering the solution by using a funnel while the solution is hot, then placing the obtained solution in the beaker, continuously heating to evaporate the solvent until a small amount of white crystals are separated out at the bottom of the solution, immediately stopping heating, slowly cooling to room temperature, separating out a large amount of white precipitates at the bottom of the beaker, filtering by using the funnel, and collecting a product; putting the obtained white or light brown solid in a vacuum drying oven to obtain TTSBI;
s22, weighing TFTPN, placing the TFTPN at the bottom of a vacuum sublimator, installing the sublimator in a fume hood with an oil bath pot and double rows of pipes, opening a vacuum pump to vacuumize the sublimator for 15min, opening the oil bath pot, slowly heating until a layer of colorless crystal-shaped product is gradually separated out at the bottom of a condensate pipe, then slowly reducing the vacuum degree in the system to standard atmospheric pressure, detaching a condenser, carefully scraping the crystallized product and collecting, and repeating the operation until no obvious residue exists in the vacuum sublimator, wherein the collected colorless crystal is the TFTPN;
s23, weighing TTSBI, TFTPN and anhydrous potassium carbonate, placing the TTSBI, TFTPN and anhydrous potassium carbonate into a round-bottom flask, adding DMF, vacuumizing the device, introducing nitrogen for protection, heating in nitrogen atmosphere, stirring at a constant speed for continuous reaction, cooling the round-bottom flask to room temperature after several days, and performing suction filtration and collection to obtain bright yellow precipitates; in order to remove anhydrous potassium carbonate which does not participate in the reaction, washing the obtained solid by deionized water, carrying out suction filtration, collecting the precipitate, placing the bright yellow product in a vacuum drying oven for drying, and repeating the process for several times; then, the purification is carried out by a methanol recrystallization method: dissolving the dried solid product in chloroform, naturally filtering with filter paper, dropwise adding the clear solution into methanol, continuously stirring, and immediately recrystallizing; filtering the separated bright yellow solid product by using a funnel, drying, repeating the operation for several times, and finally placing the obtained bright yellow precipitate in a vacuum drying box to obtain PIM-1;
s3, preparing a MOF-808@ PIM-1 membrane material:
s31, weighing the MOF-808(Zr) prepared in the step S1, placing the MOF-808(Zr) in a mortar, grinding the mixture, placing the mixture in a glass bottle, pouring trichloromethane, stirring at a constant speed, carrying out ultrasonic treatment, repeating the above processes for several times, and continuously stirring at a constant speed to obtain an MOF dispersion liquid;
s31, weighing PIM-1 solid, adding the solid into the MOF dispersion liquid prepared in the step S31 successively, and stirring until the solid is uniformly dispersed;
s32, placing a round glass culture dish on a completely horizontal top of a fume hood, slowly pouring the solution prepared in the glass bottle in the step S32 into the culture dish, covering a flat round glass plate above the culture dish to reduce the volatilization rate of the trichloromethane, standing until the solution is volatilized completely, and taking off a film at the bottom of the culture dish by using tweezers to obtain a round film;
s33, placing the round film in the step S32 in a vacuum oven, heating and continuously vacuumizing to obtain the activated MOF-808@ PIM-1 film material.
Furthermore, in S11, the mass ratio of trimesic acid, zirconium oxychloride octahydrate, deionized water, acetic acid and concentrated hydrochloric acid is 1 (4.2-4.8) (45-50) (0.4-0.5).
Furthermore, in S23, the mass ratio of TFTPN, TTSBI, anhydrous potassium carbonate and DMF is 1 (1.5-2.0): (1.0-1.5): (30-35).
Further, in S3, the mass ratio of MOF-808(Zr) to PIM-1 used was 1 (4-19).
Further, in S13, the solid product obtained in step S2 is repeatedly washed with deionized water-filtered for 3 times, placed in a glass bottle with a cover, added with 18-22mL of deionized water, stirred for 15min, then left to stand for 8h, the process is repeated for 3 times, and then repeatedly washed with ethanol-filtered for 3 times, and then filtered to collect the generated precipitate.
Further, in S22, 10g of tftpn was weighed and placed at the bottom of the vacuum sublimator, and the sublimator was mounted on the vacuum sublimator
In a fume hood with an oil bath pot and double exhaust pipes, a vacuum pump is started to vacuumize the sublimator for 15min, then the oil bath pot is opened, the temperature is slowly raised to 140-160 ℃, and the temperature is kept for 10 min.
Further, in S23, 2.56 g of TTSBI, 1.51 g of TFTPN and 2.08 g of anhydrous potassium carbonate are accurately weighed and placed in a round-bottom flask, 50 mL of DMF is added, the device is vacuumized, then nitrogen is introduced for protection, the temperature is raised to 65 ℃ under the nitrogen atmosphere, and the reaction is continuously carried out for 72 hours under uniform stirring.
Further, in S31, 0.02-0.08g of MOF-808(Zr) prepared in the step S1 is weighed, placed in a mortar, ground for 20min, placed in a glass bottle, poured with 10mL of chloroform, stirred at a constant speed for 30min, subjected to ultrasonic treatment for 10min, and repeated for 5 times, and continuously stirred at a constant speed for 12h to obtain an MOF dispersion liquid.
Further, in S32, the solution in the culture dish is left standing for 36-48 h.
The mixed matrix membrane based on the PIM-1 is prepared by the preparation method of the mixed matrix membrane based on the PIM-1 in any scheme.
The invention has the beneficial effects that:
the mixed matrix membrane MOF-808@ PIM-1 based on PIM-1 prepared by the preparation method is ethyl acetate/N2The organic metal compound has certain osmotic selectivity, and as the MOF-808 doping amount is increased to 15%, the ethyl acetate permeation rate is increased, and the osmotic selectivity is increased, so that the organic metal compound can be used for separating VOCs-containing waste gas.
Drawings
FIG. 1 is an XRD spectrum of MOF-808(Zr) in accordance with the present invention;
FIGS. 2-3 are two SEM images of MOF-808(Zr) in accordance with the present invention;
FIG. 4 shows N under 77K for PIM-1 of the present invention2An adsorption isotherm diagram;
FIG. 5 is an XRD spectrum of a MOF-808@ PIM-1 film sample of examples 1-3 herein;
FIGS. 6-9 are SEM images of film samples of comparative example 1 and examples 1-3, respectively, in sequence;
FIG. 10 is a graph showing a comparison of gas permeation separation performance of the membrane samples of examples 1 to 3 according to the present invention and comparative example 1.
Detailed Description
The technical scheme in the embodiment of the invention will be clarified by combining the attached drawings in the embodiment of the invention
Clearly, the embodiments described are only a few embodiments of the present invention, not all embodiments, which are obvious from the full description. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) The preparation process of a PIM-1 based mixed matrix membrane of this example: first, accurately weighing Zr ℃ l2 & 8H2O (1.93 g) and adding the Zr into a round-bottom flask with a magnetic stirring rod, adding deionized water (20 mL), and continuously stirring at a constant speed at normal temperature until the zirconium oxychloride octahydrate is completely dissolved. Trimesic acid (0.42 g) was weighed accurately into a round bottom flask, stirred and sonicated for 30min until completely dissolved. Acetic acid (20 mL) and concentrated hydrochloric acid (200. mu.L) were weighed accurately and added dropwise to the round-bottomed flask with stirring. Connecting the round-bottom flask with a reflux condenser pipe, connecting a balloon at the top of the reflux condenser pipe to ensure constant air pressure in the reactor, placing the round-bottom flask in an oil bath, continuously stirring at 110 ℃, and reacting for 20 hours. After the reaction was completed, it was cooled to room temperature, and the solid product was collected by centrifugation. And (3) putting the solid precipitate into a clean beaker, adding deionized water (60 mL), repeatedly washing and filtering for 3 times, and putting the product into a 120-DEG C forced air drying oven to dry for 12 hours to obtain white powder, namely a pure MOF-808(Zr) sample. Putting the MOF-808(Zr) synthesized originally into a 30 mL glass bottle with a cover, adding deionized water (20 mL), stirring for 15min, screwing the cover of the bottle, and standing for 8 h. After 8h, MOF-808(Zr) was collected by filtration, placed again in a 30 mL glass bottle with a lid, fresh deionized water (20 mL) was added, stirred for 15min and allowed to stand for 8 h. After repeating the process for 6 times, putting the sample into a dry beaker, adding absolute ethyl alcohol (60 mL) to wash for three times, and determining that the guest macromolecules in the MOF-808(Zr) pore channel are completely replaced and the activation is completed. Filtering and collecting the material, and drying the material in a vacuum drying oven at 120 ℃ for 6 h to obtain activated MOF-808 (Zr);
weighing 10.0 g of TTSBI, placing the TTSBI in a flat-bottom beaker, adding 100 mL of anhydrous methanol, stirring at a constant speed until the solid is completely dissolved, placing the beaker on a heating plate, continuously heating until the solution is boiled, filtering the solution with a funnel when the solution is hot, and removing a small amount of insoluble impurities. And then placing the obtained solution in a beaker, continuously heating to evaporate the solvent until a small amount of white crystals are separated out from the bottom of the solution, immediately stopping heating, slowly cooling to room temperature, separating out a large amount of white precipitates from the bottom of the beaker, filtering by using a funnel, and collecting the product. Putting the obtained white (or light brown) solid in a vacuum drying oven at 80 ℃ for 12h to obtain high-purity TTSBI;
weighing 10g of TFTPN, placing the TFTPN at the bottom of a vacuum sublimator, installing the sublimator in a fume hood with an oil bath pot and a double-row pipe, opening a vacuum pump to vacuumize the sublimator for 15min, opening the oil bath pot, slowly heating to 140 plus 160 ℃, keeping for 10min, and gradually separating out a layer of colorless crystal-shaped product at the bottom of a condensate pipe. After slowly reducing the degree of vacuum in the system to a standard atmospheric pressure, the condenser was removed, and the crystallized product was carefully scraped off and collected. Repeating the operation for 8-15 times until no obvious residue is left in the vacuum sublimator, and collecting colorless crystals, namely the high-purity TFTPN.
2.56 g of TTSBI, 1.51 g of TFTPN and 2.08 g of anhydrous potassium carbonate are accurately weighed, placed in a round-bottom flask, 50 mL of DMF is added, the device is vacuumized and then nitrogen is introduced for protection. Heating to 65 ℃ under the nitrogen atmosphere, and stirring at a constant speed to continuously react for 72 h. After three days, the round bottom flask was cooled to room temperature and collected by suction filtration to give a bright yellow precipitate. In order to remove unreacted K2CO3Washing the obtained solid with deionized water, filtering, collecting precipitate, drying the bright yellow product in a vacuum drying oven, and repeating the above steps for 3 times. Then, the purification is carried out by a methanol recrystallization method: the dried solid product was dissolved in chloroform (about 50 mL), filtered through filter paper, and the clear solution was added dropwise to methanol (about 150 mL) with constant stirring, and recrystallization occurred immediately. And filtering the separated bright yellow solid product by using a funnel, drying, and repeating the operation for at least three times to determine that all impurities are removed. And finally, placing the obtained bright yellow precipitate in a vacuum drying oven at 80 ℃ for 12 hours to obtain the high-purity PIM-1.
Accurately weighing 0.02g of prepared MOF-808(Zr), placing the MOF-808(Zr) in a mortar, grinding for 20min, placing the mixture in a glass bottle with a cover, pouring 10mL of trichloromethane, stirring at a constant speed for 30min, carrying out ultrasonic treatment for 10min, repeating the process for 5 times, continuously stirring at a constant speed for 12h to obtain MOF dispersion, accurately weighing 0.38g of PIM-1 solid, gradually adding the PIM-1 solid into the glass bottle, and stirring for 12h until the PIM-1 solid is completely dissolved. Placing a round glass culture dish with the diameter of 3cm on a completely horizontal table top of a fume hood, slowly pouring a solution in a glass bottle into the culture dish, covering a flat round glass plate with the diameter of 5 cm above the culture dish to control the volatilization rate of trichloromethane, standing for 48h, after the solution is volatilized, removing a thin film at the bottom of the culture dish by using forceps to obtain a round MOF-808(5%) @ PIM-1 thin film with the diameter of 3cm, wherein the mass fraction of MOF-808(Zr) is 5%, placing the thin film in a clean culture dish, placing the thin film in a vacuum oven with the temperature of 80 ℃, and continuously vacuumizing for 24h while heating, so that the MOF-808(5%) @ PIM-1 thin film material is considered to be activated completely.
(2) And (3) detection process: characterization of MOF-808@ PIM-1 membranes: performing X-ray diffraction spectrum characterization, scanning electron microscope characterization and ethyl acetate/N on the mixed matrix membrane2And (4) testing osmotic separation. When a permeation separation test is carried out, the prepared MOF-808@ PIM-1 mixed matrix membrane is placed into a mold of a permeation separation device, air containing ethyl acetate is introduced for testing, the permeation rates PEA and PN2 of the membrane to two testing gases are obtained after the test is finished, the permeation selectivity is the ratio of the permeation rates of the composite membrane to the two gases (PEA/PN 2), and the test results are shown in Table 1.
Table 1: ethyl acetate and N2Permeability rate and permselectivity
| Permeability rate of ethyl acetate (barrer) | N2Penetration Rate (barrer) | Permselectivity |
| 523.0 | 191.1 | 2.7 |
Example 2
(1) The preparation process of a PIM-1 based mixed matrix membrane of this example: first, accurately weighing 1.93 g of zirconium oxychloride octahydrate, adding the weighed zirconium oxychloride to a round-bottomed flask with a magnetic stirring rod, adding deionized water (20 mL), and continuously stirring at a constant speed at normal temperature until the zirconium oxychloride octahydrate is completely dissolved. Trimesic acid (0.42 g) was weighed accurately into a round bottom flask, stirred and sonicated for 30min until completely dissolved. Acetic acid (20 mL) and concentrated hydrochloric acid (200. mu.L) were weighed accurately and added dropwise to the round-bottomed flask with stirring. Connecting the round-bottom flask with a reflux condenser pipe, connecting a balloon at the top of the reflux condenser pipe to ensure constant air pressure in the reactor, placing the round-bottom flask in an oil bath, continuously stirring at 110 ℃, and reacting for 20 hours. After the reaction was completed, it was cooled to room temperature, and the solid product was collected by centrifugation. And (3) putting the solid precipitate into a clean beaker, adding deionized water (60 mL), repeatedly washing and filtering for 3 times, and putting the product into a 120-DEG C forced air drying oven to dry for 12 hours to obtain white powder, namely a pure MOF-808(Zr) sample. Putting the MOF-808(Zr) synthesized originally into a 30 mL glass bottle with a cover, adding deionized water (20 mL), stirring for 15min, screwing the cover of the bottle, and standing for 8 h. After 8h, MOF-808(Zr) was collected by filtration, placed again in a 30 mL glass bottle with a lid, fresh deionized water (20 mL) was added, stirred for 15min and allowed to stand for 8 h. After repeating the process for 6 times, putting the sample into a dry beaker, adding absolute ethyl alcohol (60 mL) to wash for three times, and determining that the guest macromolecules in the MOF-808(Zr) pore channel are completely replaced and the activation is completed. Filtering and collecting the material, and drying the material in a vacuum drying oven at 120 ℃ for 6 h to obtain activated MOF-808 (Zr);
weighing 10.0 g of TTSBI, placing the TTSBI in a flat-bottom beaker, adding 100 mL of anhydrous methanol, stirring at a constant speed until the solid is completely dissolved, placing the beaker on a heating plate, continuously heating until the solution is boiled, filtering the solution with a funnel when the solution is hot, and removing a small amount of insoluble impurities. And then placing the obtained solution in a beaker, continuously heating to evaporate the solvent until a small amount of white crystals are separated out from the bottom of the solution, immediately stopping heating, slowly cooling to room temperature, separating out a large amount of white precipitates from the bottom of the beaker, filtering by using a funnel, and collecting the product. Putting the obtained white (or light brown) solid in a vacuum drying oven at 80 ℃ for 12h to obtain high-purity TTSBI;
weighing 10g of TFTPN, placing the TFTPN at the bottom of a vacuum sublimator, installing the sublimator in a fume hood with an oil bath pot and a double-row pipe, opening a vacuum pump to vacuumize the sublimator for 15min, opening the oil bath pot, slowly heating to 140 plus 160 ℃, keeping for 10min, and gradually separating out a layer of colorless crystal-shaped product at the bottom of a condensate pipe. After slowly reducing the degree of vacuum in the system to a standard atmospheric pressure, the condenser was removed, and the crystallized product was carefully scraped off and collected. Repeating the operation for 8-15 times until no obvious residue is left in the vacuum sublimator, and collecting colorless crystals, namely the high-purity TFTPN.
2.56 g of TTSBI, 1.51 g of TFTPN and 2.08 g of anhydrous potassium carbonate are accurately weighed, placed in a round-bottom flask, 50 mL of DMF is added, the device is vacuumized and then nitrogen is introduced for protection. Heating to 65 ℃ under the nitrogen atmosphere, and stirring at a constant speed to continuously react for 72 h. After three days, the round bottom flask was cooled to room temperature and collected by suction filtration to give a bright yellow precipitate. In order to remove unreacted K2CO3Washing the obtained solid with deionized water, filtering, collecting precipitate, drying the bright yellow product in a vacuum drying oven, and repeating the above steps for 3 times. Then, the purification is carried out by a methanol recrystallization method: the dried solid product was dissolved in chloroform (about 50 mL), filtered through filter paper, and the clear solution was added dropwise to methanol (about 150 mL) with constant stirring, and recrystallization occurred immediately. And filtering the separated bright yellow solid product by using a funnel, drying, and repeating the operation for at least three times to determine that all impurities are removed. And finally, placing the obtained bright yellow precipitate in a vacuum drying oven at 80 ℃ for 12 hours to obtain the high-purity PIM-1.
Accurately weighing 0.04g of prepared MOF-808(Zr), placing the mixture into a mortar, grinding for 20min, placing the mixture into a glass bottle with a cover, pouring 10mL of trichloromethane, stirring at a constant speed for 30min, carrying out ultrasonic treatment for 10min, repeating the process for 5 times, continuously stirring at a constant speed for 12h to obtain MOF dispersion, accurately weighing 0.36g of PIM-1 solid, gradually adding the solid into the glass bottle, and stirring for 12h until the solid is completely dissolved. Placing a round glass culture dish with the diameter of 3cm on a completely horizontal table top of a fume hood, slowly pouring a solution in a glass bottle into the culture dish, covering a flat round glass plate with the diameter of 5 cm above the culture dish to control the volatilization rate of trichloromethane, standing for 48h, after the solution is volatilized, removing a thin film at the bottom of the culture dish by using forceps to obtain a round MOF-808(10%) @ PIM-1 thin film with the diameter of 3cm, wherein the mass fraction of the MOF-808(Zr) is 10%, placing the thin film in a clean culture dish, placing the thin film in a vacuum oven with the temperature of 80 ℃, and continuously vacuumizing for 24h while heating, so that the MOF-808(10%) @ PIM-1 thin film material is considered to be activated completely.
(2) And (3) detection process: characterization of MOF-808@ PIM-1 membranes: performing X-ray diffraction spectrum characterization, scanning electron microscope characterization and ethyl acetate/N on the mixed matrix membrane2And (4) testing osmotic separation. When a permeation separation test is carried out, the prepared MOF-808@ PIM-1 mixed matrix membrane is placed into a mold of a permeation separation device, air containing ethyl acetate is introduced for testing, the permeation rates PEA and PN2 of the membrane to two testing gases are obtained after the test is finished, the permeation selectivity is the ratio of the permeation rates of the composite membrane to the two gases (PEA/PN 2), and the test results are shown in Table 2.
Table 2: ethyl acetate and N2Permeability rate and permselectivity
| Permeability rate of ethyl acetate (barrer) | N2Penetration Rate (barrer) | Permselectivity |
| 833.3 | 175 | 4.8 |
Example 3:
(1) the preparation process comprises the following steps: first, accurately weighing 1.93 g of zirconium oxychloride octahydrate, adding the weighed zirconium oxychloride to a round-bottomed flask with a magnetic stirring rod, adding deionized water (20 mL), and continuously stirring at a constant speed at normal temperature until the zirconium oxychloride octahydrate is completely dissolved. Trimesic acid (0.42 g) was weighed accurately into a round bottom flask, stirred and sonicated for 30min until completely dissolved. Acetic acid (20 mL) and concentrated hydrochloric acid (200. mu.L) were weighed accurately and added dropwise to the round-bottomed flask with stirring. Connecting the round-bottom flask with a reflux condenser pipe, connecting a balloon at the top of the reflux condenser pipe to ensure constant air pressure in the reactor, placing the round-bottom flask in an oil bath, continuously stirring at 110 ℃, and reacting for 20 hours. After the reaction was completed, it was cooled to room temperature, and the solid product was collected by centrifugation. And (3) putting the solid precipitate into a clean beaker, adding deionized water (60 mL), repeatedly washing and filtering for 3 times, and putting the product into a 120-DEG C forced air drying oven to dry for 12 hours to obtain white powder, namely a pure MOF-808(Zr) sample. Putting the MOF-808(Zr) synthesized originally into a 30 mL glass bottle with a cover, adding deionized water (20 mL), stirring for 15min, screwing the cover of the bottle, and standing for 8 h. After 8h, MOF-808(Zr) was collected by filtration, placed again in a 30 mL glass bottle with a lid, fresh deionized water (20 mL) was added, stirred for 15min and allowed to stand for 8 h. After repeating the process for 6 times, putting the sample into a dry beaker, adding absolute ethyl alcohol (60 mL) to wash for three times, and determining that the guest macromolecules in the MOF-808(Zr) pore channel are completely replaced and the activation is completed. Filtering and collecting the material, and drying the material in a vacuum drying oven at 120 ℃ for 6 h to obtain activated MOF-808 (Zr);
weighing 10.0 g of TTSBI, placing the TTSBI in a flat-bottom beaker, adding 100 mL of anhydrous methanol, stirring at a constant speed until the solid is completely dissolved, placing the beaker on a heating plate, continuously heating until the solution is boiled, filtering the solution with a funnel when the solution is hot, and removing a small amount of insoluble impurities. And then placing the obtained solution in a beaker, continuously heating to evaporate the solvent until a small amount of white crystals are separated out from the bottom of the solution, immediately stopping heating, slowly cooling to room temperature, separating out a large amount of white precipitates from the bottom of the beaker, filtering by using a funnel, and collecting the product. Putting the obtained white (or light brown) solid in a vacuum drying oven at 80 ℃ for 12h to obtain high-purity TTSBI;
weighing 10g of TFTPN, placing the TFTPN at the bottom of a vacuum sublimator, installing the sublimator in a fume hood with an oil bath pot and a double-row pipe, opening a vacuum pump to vacuumize the sublimator for 15min, opening the oil bath pot, slowly heating to 140 plus 160 ℃, keeping for 10min, and gradually separating out a layer of colorless crystal-shaped product at the bottom of a condensate pipe. After slowly reducing the degree of vacuum in the system to a standard atmospheric pressure, the condenser was removed, and the crystallized product was carefully scraped off and collected. Repeating the operation for 8-15 times until no obvious residue is left in the vacuum sublimator, and collecting colorless crystals, namely the high-purity TFTPN.
2.56 g of TTSBI, 1.51 g of TFTPN and 2.08 g of anhydrous potassium carbonate are accurately weighed, placed in a round-bottom flask, 50 mL of DMF is added, the device is vacuumized and then nitrogen is introduced for protection. Heating to 65 ℃ under the nitrogen atmosphere, and stirring at a constant speed to continuously react for 72 h. After three days, the round bottom flask was cooled to room temperature and collected by suction filtration to give a bright yellow precipitate. In order to remove unreacted K2CO3Washing the obtained solid with deionized water, filtering, collecting precipitate, drying the bright yellow product in a vacuum drying oven, and repeating the above steps for 3 times. Then, the purification is carried out by a methanol recrystallization method: the dried solid product was dissolved in chloroform (about 50 mL), filtered through filter paper, and the clear solution was added dropwise to methanol (about 150 mL) with constant stirring, and recrystallization occurred immediately. And filtering the separated bright yellow solid product by using a funnel, drying, and repeating the operation for at least three times to determine that all impurities are removed. And finally, placing the obtained bright yellow precipitate in a vacuum drying oven at 80 ℃ for 12 hours to obtain the high-purity PIM-1.
Accurately weighing 0.06g of prepared MOF-808(Zr), placing the mixture in a mortar, grinding for 20min, placing the mixture in a glass bottle with a cover, pouring 10mL of trichloromethane, uniformly stirring for 30min, carrying out ultrasonic treatment for 10min, repeating the process for 5 times, continuously stirring for 12h at a uniform speed to obtain MOF dispersion, accurately weighing 0.34g of PIM-1 solid, gradually adding the solid into the glass bottle, and stirring for 12h until the solid is completely dissolved. Placing a round glass culture dish with the diameter of 3cm on a completely horizontal table top of a fume hood, slowly pouring a solution in a glass bottle into the culture dish, covering a flat round glass plate with the diameter of 5 cm above the culture dish to control the volatilization rate of trichloromethane, standing for 48h, after the solution is volatilized, removing a thin film at the bottom of the culture dish by using forceps to obtain a round MOF-808(15%) @ PIM-1 thin film with the diameter of 3cm, wherein the mass fraction of the MOF-808(Zr) is 15%, placing the thin film in a clean culture dish, placing the thin film in a vacuum oven with the temperature of 80 ℃, and continuously vacuumizing for 24h while heating, so that the MOF-808(15%) @ PIM-1 thin film material is considered to be activated completely.
(2) And (3) detection process: characterization of MOF-808@ PIM-1 membranes: performing X-ray diffraction spectrum characterization, scanning electron microscope characterization and ethyl acetate/N on the mixed matrix membrane2And (4) testing osmotic separation. When a permeation separation test is carried out, the prepared MOF-808@ PIM-1 mixed matrix membrane is placed into a mold of a permeation separation device, air containing ethyl acetate is introduced for testing, the permeation rates PEA and PN2 of the membrane to two testing gases are obtained after the test is finished, the permeation selectivity is the ratio of the permeation rates of the composite membrane to the two gases (PEA/PN 2), and the test results are shown in Table 3.
Table 3: ethyl acetate and N2Permeability rate and permselectivity
| Permeability rate of ethyl acetate (barrer) | N2Penetration Rate (barrer) | Permselectivity |
| 1125.2 | 158 | 7.1 |
Comparative example 1
(1) Preparation of pure PIM-1 membrane: accurately weighing 0.4g of PIM-1 solid, placing the solid in a glass bottle, adding 10mL of trichloromethane into the glass bottle, stirring for 12h until the solid is completely dissolved, placing another circular glass culture dish with the diameter of 3cm on a completely horizontal top of a fume hood, slowly pouring the solution in the glass bottle into the culture dish, covering a flat circular glass plate with the diameter of 5 cm above the culture dish to control the volatilization rate of the trichloromethane, standing for 48h, removing the film at the bottom of the culture dish by using tweezers after the solution is completely volatilized, and obtaining a circular pure PIM-1 film with the diameter of 3cm, wherein the mass fraction of MOF-808(Zr) is 0%, placing the film in a clean culture dish, placing the culture dish in a vacuum oven at 80 ℃, and continuously vacuumizing for 24h while heating, so that the pure PIM-1 film material is considered to be completely activated.
(2) Characterization of pure PIM-1 membranes: scanning Electron microscopy characterization of pure PIM-1 membranes and Ethyl acetate/N2And (4) testing osmotic separation. When a permeation separation test is carried out, the prepared pure PIM-1 membrane is placed in a mold of a permeation separation device, air containing ethyl acetate is introduced for testing, the permeation rates PEA and PN2 of the membrane to two testing gases are obtained after the test is finished, the permeation selectivity is the ratio of the permeation rates of the pure PIM-1 membrane to the two testing gases (PEA/PN 2), and the test results are shown in Table 4.
Table 4: ethyl acetate and N2Permeability rate and permselectivity
| Permeability rate of ethyl acetate (barrer) | N2Penetration Rate (barrer) | Permselectivity |
| 320.3 | 206 | 1.6 |
In summary, the following steps:
FIG. 1 is the XRD diffraction pattern of MOF-808(Zr) powder in examples 1-3, and comparing the simulated XRD diffraction pattern can find that the position of the peak in the synthesized pattern is consistent with the simulated standard pattern, which shows that we have successfully synthesized MOF-808 (Zr).
FIGS. 2-3 are SEM images of MOF-808(Zr) powder in examples 1-3, and it can be seen that the particle size of the MOF-808(Zr) particles is about 500-800 nm.
FIG. 4 shows N at 77K for PIM-1 in examples 1 to 32The adsorption isotherm diagram shows that PIM-1 has a high specific surface area.
FIG. 5 is an XRD spectrum of different types of MOF-808@ PIM-1 film samples prepared in examples 1-3, and by comparing different types of films with simulated XRD diffraction spectra, characteristic peaks of MOF-808(Zr) appear in XRD spectrums of composite films, which shows that MOF-808(Zr) particles are successfully loaded in the PIM-1 film, the intensity of the characteristic peaks of MOF-808(Zr) is increased along with the increase of doping concentration, and the crystal structure of MOF-808(Zr) is not damaged in the film forming process.
FIGS. 6 to 9 are front scanning electron micrographs of pure PIM-1 film in comparative example and different types of composite films prepared in examples 1 to 3. The composite membrane was found to be rough in surface with different sized particulate matter, presumably the incorporated MOF-808(Zr) particles. FIG. 6 shows comparative example 1 (reference a), FIG. 7 shows example 1 (reference b), FIG. 8 shows example 2 (reference c), and FIG. 9 shows example 3 (reference d).
FIG. 10 is a graph showing the differential pressure between the two sides of the composite membranes of examples 1-3 at a test temperature of 25 deg.C and a pressure of 0.05 MPaEthyl acetate concentration of 1000ppm2Comparative permeation performance of (c). The graph shows that the MOF-808@ PIM-1 composite membrane with different MOF doping amounts is opposite to ethyl acetate/N2There is a certain selectivity. As the MOF-808(Zr) incorporation amount is increased, the permeation rate of ethyl acetate is increased, and the permeation selectivity is increased.
In order to determine the doping amount of MOF-808(Zr) in the composite membrane, the prepared composite membrane can show more excellent ethyl acetate/N2Separation Performance pure PIM-1 membranes, MOF-808(5%) @ PIM-1, MOF-808(10%) @ PIM-1, MOF-808(15%) @ PIM-1, respectively, without and with doping amounts of 5%, 10%, 15% MOF-808(Zr) were prepared according to the conditions in Table 1.
Table 5: composition conditions of different composite membranes
It can be seen that the separation and recovery of organic vapors from waste gas streams using membranes made in accordance with the present invention is an efficient and safe process with the advantages of no pollution, convenient operation and low energy consumption.
The invention relates to relevant test conditions and methods:
x-ray photoelectron diffraction (XRD) spectrum: the XRD test used was an XRD-6000X-ray diffractometer from Shimadzu corporation, Japan. The Cu emission field was used, and the 2theta range was scanned at 5-40 deg..
Scanning Electron Microscope (SEM) photograph: the SEM used a SU8010 field emission scanning electron microscope from Hitachi, Japan.
N2Adsorption isotherm diagram: n is a radical of2Adsorption used was an ASAP 2460 surface area and pore size analyzer from shanghai macrmericek instruments.
In the gas separation test, an SPG-AT01 VOC generator (containing a precision injector) from Arois, Suzhou was used to generate ethyl acetate vapor, and the mixed gas of ethyl acetate vapor and air was fed into the membrane module under the control of a flow meter, and the pressure difference across the membrane was controlled by a back pressure valve AT the outlet end. The gas that permeates is collected by the gas sampling bag, gets into gas chromatography and inspects various gas content in order to confirm the separation effect, and tail gas absorbs or the condensation is retrieved.
Gas Chromatography (GC) analysis: GC-7890B gas chromatograph from Agilent technologies, USA and A91Plus high-end laboratory gas chromatograph from Tokya.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a mixed matrix membrane based on PIM-1 is characterized by comprising the following steps:
s1, preparing MOF-808(Zr) crystals:
s11, firstly, dissolving trimesic acid and zirconium oxychloride octahydrate in deionized water, adding acetic acid and concentrated hydrochloric acid, and sealing in a heating, condensing and refluxing device;
s12, placing the round-bottom flask which is heated in the condensation reflux device in the S11 into an oil bath for continuous reaction, slowly cooling to room temperature after the reaction is finished, and filtering and collecting a generated solid product;
s13, repeatedly washing and filtering the solid product obtained in the step S12 by using deionized water for several times, placing the solid product into a glass bottle, adding the deionized water, stirring, standing, repeating the process for several times, repeatedly washing and filtering by using ethanol for several times, and filtering to collect a generated precipitate product;
s14, placing the precipitation product obtained in the step S13 in a blast drying oven for drying, and obtaining MOF-808(Zr) crystals;
s2, PIM-1 preparation:
s21, weighing TTSBI, placing the TTSBI in a flat-bottom beaker, adding anhydrous methanol, stirring at a constant speed until the solid is completely dissolved, placing the beaker on a heating plate, continuously heating until the solution is boiled, filtering the solution by using a funnel while the solution is hot, then placing the obtained solution in the beaker, continuously heating to evaporate the solvent until a small amount of white crystals are separated out at the bottom of the solution, immediately stopping heating, slowly cooling to room temperature, separating out a large amount of white precipitates at the bottom of the beaker, filtering by using the funnel, and collecting a product; putting the obtained white or light brown solid in a vacuum drying oven to obtain TTSBI;
s22, weighing TFTPN, placing the TFTPN at the bottom of a vacuum sublimator, installing the sublimator in a fume hood with an oil bath pot and double rows of pipes, opening a vacuum pump to vacuumize the sublimator for 15min, opening the oil bath pot, slowly heating until a layer of colorless crystal-shaped product is gradually separated out at the bottom of a condensate pipe, then slowly reducing the vacuum degree in the system to standard atmospheric pressure, detaching a condenser, carefully scraping the crystallized product and collecting, and repeating the operation until no obvious residue exists in the vacuum sublimator, wherein the collected colorless crystal is the TFTPN;
s23, weighing TTSBI, TFTPN and anhydrous potassium carbonate, placing the TTSBI, TFTPN and anhydrous potassium carbonate into a round-bottom flask, adding DMF, vacuumizing the device, introducing nitrogen for protection, heating in nitrogen atmosphere, stirring at a constant speed for continuous reaction, cooling the round-bottom flask to room temperature after several days, and performing suction filtration and collection to obtain bright yellow precipitates; in order to remove anhydrous potassium carbonate which does not participate in the reaction, washing the obtained solid by deionized water, carrying out suction filtration, collecting the precipitate, placing the bright yellow product in a vacuum drying oven for drying, and repeating the process for several times; then, the purification is carried out by a methanol recrystallization method: dissolving the dried solid product in chloroform, naturally filtering with filter paper, dropwise adding the clear solution into methanol, continuously stirring, and immediately recrystallizing; filtering the separated bright yellow solid product by using a funnel, drying, repeating the operation for several times, and finally placing the obtained bright yellow precipitate in a vacuum drying box to obtain PIM-1;
s3, preparing a MOF-808@ PIM-1 membrane material:
s31, weighing the MOF-808(Zr) prepared in the step S1, placing the MOF-808(Zr) in a mortar, grinding the mixture, placing the mixture in a glass bottle, pouring trichloromethane, stirring at a constant speed, carrying out ultrasonic treatment, repeating the above processes for several times, and continuously stirring at a constant speed to obtain an MOF dispersion liquid;
s31, weighing PIM-1 solid, adding the solid into the MOF dispersion liquid prepared in the step S31 successively, and stirring until the solid is uniformly dispersed;
s32, placing a round glass culture dish on a completely horizontal top of a fume hood, slowly pouring the solution prepared in the glass bottle in the step S32 into the culture dish, covering a flat round glass plate above the culture dish to reduce the volatilization rate of the trichloromethane, standing until the solution is volatilized completely, and taking off a film at the bottom of the culture dish by using tweezers to obtain a round film;
s33, placing the round film in the step S32 in a vacuum oven, heating and continuously vacuumizing to obtain the activated MOF-808@ PIM-1 film material.
2. The method of claim 1, wherein the mass ratio of the trimesic acid, the zirconium oxychloride octahydrate, the deionized water, the acetic acid and the concentrated hydrochloric acid in S11 is 1 (4.2-4.8): (45-50): 0.4-0.5.
3. The method for preparing the PIM-1-based mixed matrix membrane according to claim 1, wherein the mass ratio of TFTPN, TTSBI, anhydrous potassium carbonate and DMF in S23 is 1 (1.5-2.0) to (1.0-1.5) to (30-35).
4. The method for preparing the PIM-1-based mixed matrix membrane according to claim 1, wherein the mass ratio of MOF-808(Zr) to PIM-1 used in S3 is 1 (4-19).
5. The method for preparing a PIM-1 based mixed matrix membrane as claimed in claim 1, wherein the solid product obtained in the step S2 is washed and filtered repeatedly with deionized water for 3 times in S13, and then placed in a glass bottle with a cover, 18-22mL of deionized water is added, the mixture is stirred for 15min, then left to stand for 8h, the process is repeated for 3 times, and then washed and filtered repeatedly with ethanol for 3 times, and then the resulting precipitate is collected by filtration.
6. The method for preparing the PIM-1-based mixed matrix membrane according to claim 1, wherein 10g of TFTPN is weighed and placed at the bottom of the vacuum sublimator in S22, the sublimator is installed in a fume hood with an oil bath and a double-row pipe, the oil bath is opened after the vacuum pump is turned on to vacuumize the sublimator for 15min, and the temperature is slowly raised to 140-.
7. The method for preparing the mixed matrix membrane based on the PIM-1 as claimed in claim 1, wherein in S23, 2.56 g of TTSBI, 1.51 g of TFTPN and 2.08 g of anhydrous potassium carbonate are accurately weighed and placed in a round bottom flask, 50 mL of DMF is added, the device is vacuumized and then is filled with nitrogen for protection, the temperature is raised to 65 ℃ under nitrogen atmosphere, and the reaction is continuously carried out for 72 hours under uniform stirring.
8. The preparation method of the PIM-1-based mixed matrix membrane according to claim 1, wherein in S31, 0.02-0.08g of MOF-808(Zr) prepared in the step S1 is weighed and put in a mortar, ground for 20min, put in a glass bottle, poured with 10mL of chloroform, stirred at a constant speed for 30min, sonicated for 10min, and after repeating the above process for 5 times, stirred at a constant speed for 12h to obtain the MOF dispersion.
9. The method for preparing a PIM-1-based mixed matrix membrane as set forth in claim 1, wherein the solution in the culture dish is left to stand for a period of 36 to 48 hours in S32.
10. A PIM-1 based mixed matrix membrane prepared by the method for preparing a PIM-1 based mixed matrix membrane according to any one of claims 1 to 9.
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