CN117123053A - High-temperature-resistant hollow fiber ultrafiltration membrane based on metal organic framework MIL-53 (Fe) and preparation method thereof - Google Patents
High-temperature-resistant hollow fiber ultrafiltration membrane based on metal organic framework MIL-53 (Fe) and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 96
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 72
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 69
- 239000013206 MIL-53 Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 title claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000005266 casting Methods 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 19
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 10
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920006254 polymer film Polymers 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920005597 polymer membrane Polymers 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims 2
- 238000005345 coagulation Methods 0.000 claims 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 44
- 230000014759 maintenance of location Effects 0.000 abstract description 36
- 108091003079 Bovine Serum Albumin Proteins 0.000 abstract description 31
- 229940098773 bovine serum albumin Drugs 0.000 abstract description 31
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000004907 flux Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000001891 gel spinning Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003361 porogen Substances 0.000 description 6
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- 239000004743 Polypropylene Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000004941 mixed matrix membrane Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RAYLUPYCGGKXQO-UHFFFAOYSA-N n,n-dimethylacetamide;hydrate Chemical compound O.CN(C)C(C)=O RAYLUPYCGGKXQO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/18—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The invention discloses a high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) and a preparation method thereof, belonging to the technical field of membrane separation. 49.5 to 78.8 percent (w/w) of solvent, 9.0 to 18.0 percent (w/w) of pore-forming agent and 0.1 percentAdding surfactant (w/w) of which the concentration is between percent and 2.0 percent into a dissolving tank respectively according to a certain sequence, and stirring uniformly at normal temperature; adding 0.1-3.5% (w/w) MIL-53 (Fe) and stirring at 30-90 deg.C for 1-3 hr. Then adding polysulfone or polyethersulfone with the concentration of 12.0-27.0% (w/w) into a dissolving tank, stirring and dissolving for 6-12 hours at the temperature of 30-90 ℃ to completely dissolve, standing and defoaming for 8-24 hours to prepare casting film liquid; and preparing the high-temperature-resistant hollow fiber ultrafiltration membrane by adopting a traditional dry-wet spinning process. The pure water flux of the ultrafiltration membrane prepared by the invention is more than or equal to 330L/m 2 Hr.0.1 MPa, bovine serum albumin retention rate not less than 95.00%; after being treated in deionized water at 100 ℃ for 60min, the pure water permeability coefficient and the bovine serum albumin retention rate of the agent are not changed greatly, which indicates that the agent has good high temperature resistance.
Description
Technical Field
The invention relates to a macromolecule mixed matrix ultrafiltration membrane and a preparation method thereof, in particular to a high-temperature-resistant hollow fiber ultrafiltration membrane based on a metal organic framework MIL-53 (Fe) and a preparation method thereof.
Background
The lack of water resources and the increasingly serious water pollution have become bottlenecks limiting social progress and economic development, and the recycling of waste water and sewage has become a global general concern. Due to the high-speed development of economy, a large amount of waste water is generated, and sewage reclamation has become a strategic choice for solving the water resource crisis. Among the many sewage recycling technologies, membrane separation technology is one of the best options. In the field of industrial water treatment, the water temperature of a lot of waste water is higher, and because the conventional ultrafiltration membrane product can only run below 45 ℃, the waste water needs to be subjected to cooling post-treatment by different means, the energy consumption loss is caused, and the waste water treatment cost is increased. Therefore, there is a great need to develop a high temperature resistant hollow fiber ultrafiltration membrane to meet the requirements of high temperature wastewater treatment.
The mixed matrix membrane is a membrane formed by chemically crosslinking or microcosmically mixing organic and inorganic components, is also called as an organic-inorganic hybrid membrane, and has the advantages of corrosion resistance, heat resistance, high separability and toughness of an organic membrane and the like, so that the mixed matrix membrane becomes one of hot spots for researching the modification of membrane materials. Metal-organic frameworks (Metal-Organic Frameworks, MOFs) are a porous material with an infinite network structure; compared with the traditional inorganic porous material, the MOFs material has incomparable excellent performance of inorganic porous materials such as zeolite, active carbon, carbon nano tube and the like, has micropore volume which is several times higher than that of the porous material, and has the characteristics of changeable pore canal, stable chemical structure and the like; the excellent characteristics lead the MOFs material to have great application prospect in the aspects of gas storage, water pollutant adsorption separation, gas catalysis and the like. Meanwhile, as a novel organic-inorganic hybrid material, the organic ligand in the metal-organic framework structure is favorable for improving the affinity between MOFs particles and a polymer matrix, and is an ideal mixed matrix membrane disperse phase. Therefore, if a proper MOFs material and a polymer membrane material are blended to prepare the mixed matrix ultrafiltration membrane, the ultrafiltration membrane product is expected to have high water flux, high rejection rate, high temperature resistance, high pollution resistance and high mechanical strength, and a new thought is provided for research, development, application and popularization of the mixed matrix ultrafiltration membrane.
At present, researchers at home and abroad prepare high-temperature resistant separation membranes by treating high-molecular-group membranes. The invention patent ZL201810614366.6 introduces nano particles into the hollow fiber base membrane by a crosslinking method to enable the hollow fiber base membrane to have temperature resistance; according to the invention, the PASS ultrathin filtration compact layer is prepared by coating the inner wall of a PP substrate tube by a phase inversion method by using a porous PP material as a supporting substrate of the tubular membrane, so that the high-flux PASS/PP tubular ultrafiltration membrane with good acid-base resistance and high temperature resistance is prepared; the invention patent ZL202011401689.0 carries out grafting modification on a polypropylene base film so that the upper surface and the lower surface are respectively coated with a layer of modified film, thus preparing a high-temperature resistant modified filter film; the invention improves the temperature resistance of the separation membrane, but the preparation process is more complex. The structure of the hollow fiber ultrafiltration membrane is improved by adopting a metal organic framework MIL-53 (Fe) blending method, the membrane forming process is simplified, and the researches on the temperature resistance, the mechanical property, the permeability and the separation performance of the mixed matrix ultrafiltration membrane are improved, and have not been reported in the literature at home and abroad; in addition, the preparation of the high-temperature-resistant hollow fiber mixed matrix ultrafiltration membrane and industrialization are realized, the production of similar high-temperature-resistant hollow fiber ultrafiltration membrane products is not seen at home and abroad, and related literature reports are not yet seen at home and abroad.
Disclosure of Invention
To solve the above technical problems, a first object of the present invention is to provide a high temperature resistant hollow fiber ultrafiltration membrane based on a metal organic framework MIL-53 (Fe), and another object of the present invention is to provide a method for preparing the same.
In order to achieve the first object, the present invention adopts the following technical scheme:
a high-temperature-resistant hollow fiber ultrafiltration membrane based on a metal organic framework MIL-53 (Fe) comprises the following substances in percentage by mass: 12.0 to 27.0 percent (w/w) of polymer film material, 9.0 to 18.0 percent (w/w) of pore-forming agent, 0.1 to 2.0 percent (w/w) of surfactant, 0.1 to 3.5 percent (w/w) of metal organic framework MIL-53 (Fe) and 49.5 to 78.8 percent (w/w) of solvent;
the polymer membrane material is one or two of polyethersulfone and polysulfone, and the content is 12.0% -27.0% (w/w);
the pore-forming agent is one of polyethylene glycol 400 and polyvinylpyrrolidone, and the content is 9.0% -18.0% (w/w);
the surfactant is a nonionic surfactant, such as polysorbate (tween) -80 and the like, and the content is 0.1% -2.0% (w/w);
the MIL-53 (Fe) of the metal organic framework is an irregular polyhedral nano material with a smooth surface, and the content is 0.1% -3.5% (w/w);
the solvent is one or two of N, N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP), and the content is 49.5% -78.8% (w/w).
A preparation method of a high-temperature-resistant hollow fiber ultrafiltration membrane based on a metal organic framework MIL-53 (Fe) comprises the following steps:
(1) Respectively adding a certain amount of solvent, pore-forming agent and surfactant into a dissolving tank according to a certain proportion in sequence, and uniformly stirring at normal temperature; then adding a certain proportion of metal organic framework MIL-53 (Fe) into a dissolving tank, and stirring for 1-3 hours at the temperature of 30-90 ℃ until the mixture is uniformly dispersed;
(2) Adding a certain amount of polymer film material into a dissolution tank, stirring and dissolving for 6-12 hours at the temperature of 30-90 ℃ until the polymer film material is completely dissolved, and preparing initial film casting liquid; then standing the obtained casting film liquid at a certain temperature for 8-24 hours to completely defoam the casting film liquid;
(3) The traditional phase inversion spinning process is adopted, the casting solution flow rate is controlled to be 5.0-25.0 mL/min, the casting solution temperature is 30-70 ℃, the coagulating bath temperature is 15-30 ℃, the height between air is 0-15 cm, and the hollow fiber membrane coagulating time is 0.5-3.0 min, so that the high temperature resistant hollow fiber ultrafiltration membrane is prepared;
(4) Finally, the prepared hollow fiber membrane is put into deionized water to be soaked and washed for 16 to 24 hours, so as to clean the additive; then the mixture is put into a glycerol solution with the concentration of 50 percent to be treated for 24 to 48 hours, thus preparing the high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) of the metal organic framework.
The coagulating bath is 5.0-15.0% (w/w) of N, N-dimethylacetamide aqueous solution.
The invention provides a high-temperature-resistant hollow fiber ultrafiltration membrane based on a metal organic framework MIL-53 (Fe) and a preparation method thereof, wherein MIL-53 (Fe) is introduced into a polymer to prepare a mixed matrix ultrafiltration membrane, and the mixed matrix ultrafiltration membrane is endowed with good high-temperature resistance. In order to test the temperature resistance of the prepared high-temperature-resistant hollow fiber ultrafiltration membrane, the invention tests the prepared ultrafiltration membrane. The result shows that after the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is placed in deionized water at 100 ℃ for 60 minutes, the pure water permeability coefficient is 335.27L/square meter hr-0.1 MPa, the bovine serum albumin (67000 MW) retention rate is 96.29%, and the change is small compared with the change before the treatment, thus showing that the high-temperature-resistant performance is good.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the traditional polysulfone and polyethersulfone ultrafiltration membranes, the high-temperature-resistant hollow fiber ultrafiltration membrane prepared by blending and modifying the MIL-53 (Fe) of the metal organic framework provided by the invention has greatly improved high-temperature resistance and pollution resistance.
(2) The method for preparing the high-temperature-resistant hollow fiber ultrafiltration membrane by blending and modifying the MIL-53 (Fe) of the metal organic framework provided by the invention has the advantages that the equipment is as simple as the traditional hollow fiber ultrafiltration membrane spinning equipment, the control is easy, the membrane preparation process is simple, the high-temperature resistance and the pollution resistance of the prepared ultrafiltration membrane are endowed while the membrane is formed, and the industrialization is easy to realize.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1:
adding 63.5% (w/w) of N, N-dimethylacetamide, 15.0% (w/w) of polyethylene glycol 400 and 1.0% (w/w) of Tween 80 into a dissolution tank respectively according to the sequence, and stirring for 0.5 hours at normal temperature until the materials are uniformly dispersed; and continuously maintaining the normal temperature, adding MIL-53 (Fe) of a metal organic frame with the total amount of 1.5% (w/w) of the casting solution, and stirring at the temperature of 80 ℃ for 1.5 hours until the mixture is uniformly dispersed. Then, adding 19.0% (w/w) of polyethersulfone into a dissolution tank, stirring and dissolving at 80 ℃ for 8 hours until the polyethersulfone is completely dissolved, and preparing a casting solution; finally, the obtained casting solution was left standing still at 65℃for 12 hours to completely defoam the casting solution.
The casting solution flow rate is controlled to be 12.0mL/min, the casting solution temperature is 65 ℃, the coagulating bath (15.0% (w/w) N, N-dimethylacetamide water solution) temperature is 25 ℃, the height between air is 3.5cm, the hollow fiber membrane coagulating time is 1.0 min, and the high temperature resistant polyether sulfone hollow fiber ultrafiltration membrane is prepared by adopting the traditional phase inversion spinning process. The prepared hollow fiber membrane is put into deionized water to be washed for 24 hours so as to clean the additive; then placing the mixture into a 50% (w/w) glycerol solution for treatment for 36 hours, and preparing the MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane; the pure water permeability coefficient is 337.51L/square meter hr.0.1 MPa, and the bovine serum albumin (67000 MW) retention rate is 96.25%. After the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is placed in deionized water at 100 ℃ for 60min, the pure water permeability coefficient is 335.27L/square meter hr-0.1 MPa, the bovine serum albumin (67000 MW) retention rate is 96.29%, and the change is small compared with that before the treatment, so that the high-temperature-resistant hollow fiber ultrafiltration membrane has good high-temperature resistance.
Example 2:
the MIL-53 (Fe) content of the metal organic frame was reduced from 1.5% (w/w) to 0.1% (w/w), the dimethylacetamide content was reduced from 63.5% (w/w) to 57.8% (w/w), the polyethersulfone content was increased to 27%, and the Tween-80 content was reduced to 0.1%, the remainder being as in example 1. The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 229.36L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 95.43%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 210.15L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 95.97%; compared with the prior treatment, the pure water permeability coefficient is reduced by 8.39%, and the retention rate is improved by 0.57%.
Example 3:
the content of MIL-53 (Fe) in the metal organic frame was increased from 1.5% (w/w) to 3.5% (w/w), the content of dimethylacetamide was increased from 63.5% (w/w) to 67.5% (w/w), the content of Tween-80 was increased to 2.0%, the content of polyethersulfone was decreased to 12%, and the rest was the same as in example 1. The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 312.83L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 95.92%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 309.41L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 96.14%; compared with the prior treatment, the pure water permeability coefficient is reduced by 1.09%, and the retention rate is improved by 0.23%.
Example 4:
the remainder of example 1 was followed with the substitution of the polymeric membrane material with polysulfone from polyethersulfone. The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 276.53L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 95.49%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 273.79L/square meter hr-0.1 MPa, and the bovine serum albumin retention rate is 95.86%; compared with the prior treatment, the pure water permeability coefficient is reduced by 0.99 percent, and the retention rate is improved by 0.39 percent.
Example 5:
the procedure of example 4 was repeated except that the MIL-53 (Fe) content of the metal-organic framework was reduced from 1.5% (w/w) to 0.1% (w/w), and the dimethylacetamide content was increased from 63.5% (w/w) to 64.9% (w/w). The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 189.22L/square meter hr.0.1 MPa, and the bovine serum albumin rejection rate is 95.12%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 172.06L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 95.71%; compared with the prior treatment, the pure water permeability coefficient is reduced by 9.07 percent, and the retention rate is improved by 0.62 percent.
Example 6:
the procedure of example 4 was repeated except that the MIL-53 (Fe) content of the metal-organic framework was increased from 1.5% (w/w) to 3.5% (w/w), and the dimethylacetamide content was decreased from 63.5% (w/w) to 61.5% (w/w). The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 256.95L/square meter hr.0.1 MPa, and the bovine serum albumin rejection rate is 95.37%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 251.54L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 95.68%; compared with the prior treatment, the pure water permeability coefficient is reduced by 2.11 percent, and the retention rate is improved by 0.33 percent.
Example 7:
the content of the porogen polyethylene glycol 400 was reduced from 15.0% (w/w) to 9.0% (w/w), and the content of dimethylacetamide was increased from 63.5% (w/w) to 69.5% (w/w), the remainder being as in example 1. The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 306.64L/square meter hr.0.1 MPa, and the bovine serum albumin rejection rate is 95.07%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 304.69L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 95.33%; compared with the prior treatment, the pure water permeability coefficient is reduced by 0.57 percent, and the retention rate is improved by 0.27 percent.
Example 8:
the content of the porogen polyethylene glycol 400 was increased from 15.0% (w/w) to 18.0% (w/w), and the content of dimethylacetamide was decreased from 63.5% (w/w) to 60.5% (w/w), the remainder being as in example 1. The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 332.15L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 94.36%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 327.92L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 94.81%; compared with the prior treatment, the pure water permeability coefficient is reduced by 1.27%, and the retention rate is improved by 0.48%.
Example 9:
the porogen was replaced by polyvinylpyrrolidone from polyethylene glycol 400, the remainder being as in example 1. The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 322.19L/square meter hr.0.1 MPa, and the bovine serum albumin rejection rate is 96.14%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 320.53L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 96.38%; compared with the prior treatment, the pure water permeability coefficient is reduced by 0.52 percent, and the retention rate is improved by 0.25 percent.
Example 10:
the remainder of example 1 was followed by substituting polyethersulfone for polysulfone and polyethylene glycol 400 for polyvinylpyrrolidone for the porogen. The pure water permeability coefficient of the prepared MIL-53 (Fe) -based high-temperature-resistant hollow fiber ultrafiltration membrane is 271.91L/square meter hr.0.1 MPa, and the bovine serum albumin rejection rate is 95.83%. The prepared high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) is placed in deionized water at 100 ℃ for 60min, and then the pure water permeability coefficient is 269.72L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 96.18%; compared with the prior treatment, the pure water permeability coefficient is reduced by 0.81 percent, and the retention rate is improved by 0.37 percent.
Comparative example 1:
65.0% (w/w) of N, N-dimethylacetamide, 15.0% (w/w) of polyethylene glycol 400 and 1.0% (w/w) of Tween 80 are respectively added into a dissolution tank according to a certain sequence, and stirred at 80 ℃ for 0.5 hours until the materials are uniformly dispersed. Then, adding 19.0% (w/w) of polyethersulfone into a dissolution tank, stirring and dissolving at 80 ℃ for 8 hours until the polyethersulfone is completely dissolved, and preparing a casting solution; finally, the obtained casting solution was left standing still at 65℃for 12 hours to completely defoam the casting solution.
Controlling the casting solution flow rate to be 12.0mL/min, controlling the casting solution temperature to be 65 ℃, the coagulating bath (deionized water) temperature to be 25 ℃, the height between air to be 3.5cm, and the hollow fiber membrane coagulating time to be 1.0 min, and preparing the polyether sulfone hollow fiber ultrafiltration membrane by adopting the traditional phase inversion spinning process. The prepared hollow fiber membrane is put into deionized water to be washed for 24 hours so as to clean the additive; then placing the mixture into a glycerol solution with the concentration of 50% (w/w) for treatment for 36 hours, and preparing the polyether sulfone hollow fiber ultrafiltration membrane; the pure water permeability coefficient is 213.73L/square meter hr.0.1 MPa, and the bovine serum albumin (67000 MW) retention rate is 95.39%. After the prepared polyether sulfone hollow fiber ultrafiltration membrane is placed in deionized water at 100 ℃ for 60min, the pure water permeability coefficient is 185.32L/square meter hr-0.1 MPa, and the bovine serum albumin (67000 MW) retention rate is 96.78%; compared with the prior treatment, the pure water permeability coefficient is reduced by 13.29 percent, and the retention rate is improved by 1.46 percent.
Comparative example 2:
the polymer membrane material was replaced with polysulfone from polyethersulfone and the remainder was the same as comparative example 1. The pure water permeability coefficient of the prepared polysulfone hollow fiber ultrafiltration membrane is 179.56L/square meter hr.0.1 MPa, and the bovine serum albumin rejection rate is 94.69%. The prepared polysulfone hollow fiber ultrafiltration membrane is placed in deionized water at 100 ℃ for 60 minutes, and then the pure water permeability coefficient is 153.95L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 96.12%; compared with the prior treatment, the pure water permeability coefficient is reduced by 14.26 percent, and the retention rate is improved by 1.51 percent.
Comparative example 3:
the porogen was replaced by polyvinylpyrrolidone from polyethylene glycol 400 and the remainder was the same as in comparative example 1. The pure water permeability coefficient of the prepared polyethersulfone hollow fiber ultrafiltration membrane is 205.61L/square meter hr.0.1 MPa, and the rejection rate of bovine serum albumin (67000 MW) is 95.77%. After the prepared polyether sulfone hollow fiber ultrafiltration membrane is placed in deionized water at 100 ℃ for 60min, the pure water permeability coefficient is 182.25L/square meter hr-0.1 MPa, and the bovine serum albumin (67000 MW) retention rate is 96.93%; compared with the prior treatment, the pure water permeability coefficient is reduced by 11.36 percent, and the retention rate is improved by 1.21 percent.
Comparative example 4:
the polymer membrane material is replaced by polysulfone, the porogen is replaced by polyvinylpyrrolidone by polyethylene glycol 400, and the rest is the same as in comparative example 1. The pure water permeability coefficient of the prepared polysulfone hollow fiber ultrafiltration membrane is 165.37L/square meter hr.0.1 MPa, and the bovine serum albumin rejection rate is 95.26%. The prepared polysulfone hollow fiber ultrafiltration membrane is placed in deionized water at 100 ℃ for 60 minutes, and then the pure water permeability coefficient is 144.66L/square meter hr.0.1 MPa, and the bovine serum albumin retention rate is 96.53%; compared with the prior treatment, the pure water permeability coefficient is reduced by 12.52 percent, and the retention rate is improved by 1.33 percent.
Claims (5)
1. The high-temperature-resistant hollow fiber ultrafiltration membrane based on the metal organic framework MIL-53 (Fe) is characterized by being prepared from the following substances in percentage by mass:
12.0 to 27.0 percent of polymer film material
Pore-forming agent 9.0-18.0%
0.1 to 2.0 percent of surfactant
MIL-53 (Fe) of metal organic frame 0.1-3.5%
The balance being solvent.
2. The high temperature resistant hollow fiber ultrafiltration membrane based on metal organic frameworks MILs-53 (Fe) of claim 1, wherein:
the polymer membrane material is polyethersulfone or polysulfone;
the pore-forming agent is one of polyethylene glycol 400 and polyvinylpyrrolidone;
the surfactant is non-ionic surfactant Tween-80.
3. The high temperature resistant hollow fiber ultrafiltration membrane based on metal organic frameworks MILs-53 (Fe) of claim 1, wherein:
the solvent is one or two of N, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
4. A preparation method of a high-temperature-resistant hollow fiber ultrafiltration membrane based on a metal organic framework MIL-53 (Fe) is characterized by comprising the following steps:
step (1) adding a solvent, a pore-forming agent and a surfactant into a dissolution tank in proportion and sequence, and uniformly stirring at normal temperature; then adding MIL-53 (Fe) of a metal organic framework into a dissolving tank, and stirring for 1-3 hours at the temperature of 30-90 ℃ until the mixture is uniformly dispersed;
step (2) adding a polymer film material into a dissolution tank, stirring and dissolving for 6-12 hours at the temperature of 30-90 ℃ until the polymer film material is completely dissolved, and preparing initial film casting liquid; then standing the obtained casting solution at 65 ℃ for 8-24 hours to completely defoam the casting solution, thus obtaining the high-temperature-resistant hollow fiber ultrafiltration membrane casting solution;
step (3) adopts a traditional phase inversion spinning process, the casting solution flow rate is controlled to be 5.0-25.0 mL/min, the casting solution temperature is 30-70 ℃, the coagulation bath temperature is 15-30 ℃, the height between air is 0-15 cm, the coagulation time of the hollow fiber membrane is 0.5-3.0 min, and the high-temperature-resistant hollow fiber ultrafiltration membrane is prepared;
step (4) putting the prepared hollow fiber membrane into deionized water for soaking and washing for 16-24 hours to clean the additive; then the mixture is put into a glycerol solution with the concentration of 50 percent to be treated for 24 to 48 hours, thus preparing the high-temperature-resistant hollow fiber ultrafiltration membrane based on MIL-53 (Fe) of the metal organic framework.
5. The method for preparing the high-temperature-resistant hollow fiber ultrafiltration membrane based on the metal organic framework MIL-53 (Fe) is characterized by comprising the following steps of: the coagulating bath is 5.0-15.0% of N, N-dimethylacetamide aqueous solution.
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