CN117123063A - High-strength hollow fiber ultrafiltration membrane and preparation method thereof - Google Patents
High-strength hollow fiber ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN117123063A CN117123063A CN202311185083.1A CN202311185083A CN117123063A CN 117123063 A CN117123063 A CN 117123063A CN 202311185083 A CN202311185083 A CN 202311185083A CN 117123063 A CN117123063 A CN 117123063A
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- 239000012528 membrane Substances 0.000 title claims abstract description 49
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 43
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 1, 10-phenanthroline modified ZIF-8 Chemical class 0.000 claims abstract description 34
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 12
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims description 67
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 16
- 108091003079 Bovine Serum Albumin Proteins 0.000 abstract description 11
- 229940098773 bovine serum albumin Drugs 0.000 abstract description 11
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 62
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 8
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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
- B01D69/08—Hollow fibre membranes
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- 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
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the field of composite materials, and in particular relates to a high-strength hollow fiber ultrafiltration membrane and a preparation method thereof, wherein 24.5 parts of diethylene glycol is slowly added into 54 parts of dimethylacetamide according to parts by weight, 1, 10-phenanthroline modified ZIF-8/Fe complex or 1, 10-phenanthroline modified ZIF-8/Fe/CeO are added at a stirring speed of 500r/min 2 Stirring one of the compounds for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under a nitrogen atmosphere at a stirring speed of 500r/min; then naturally cooling to 30 ℃, maintaining the vacuum defoamation at 30 ℃ for one day, and the hollow fiber ultrafiltration membrane prepared by the invention solves the problem that the Z is modified by using 1, 10-phenanthrolineThe IF-8/Fe complex causes the problem that the retention rate of the hollow fiber ultrafiltration membrane to bovine serum albumin is too low, and the retention rate to bovine serum albumin and higher pure water flux are maintained while the tensile strength is improved.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a high-strength hollow fiber ultrafiltration membrane and a preparation method thereof.
Background
The ultrafiltration technology is membrane filtration, and the specific pore diameter of 0.01-0.1 um of the ultrafiltration membrane can effectively intercept bacteria, viruses, colloids and the like, thereby achieving the purposes of separation, classification, purification and concentration.
The ultrafiltration process has the characteristics of no phase change, simple operation and the like, and is widely applied to the fields of water treatment, food industry, biochemical industry and the like. As ultrafiltration technology advances, its contribution to human society will also increase.
The hollow fiber ultrafiltration membrane has the advantages of large filling density, easy control of the production process and low production cost, and becomes a main form of the ultrafiltration membrane, and is the main stream of the current market.
The ultrafiltration membrane is mainly made of PVDF, PES, PS, PVC, PAN, PP. In the prior art, ZIF-8 is added into the PES ultrafiltration membrane, so that the water flux of the ultrafiltration membrane is improved, but the strength of membrane filaments is still required to be improved.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a high-strength hollow fiber ultrafiltration membrane and a preparation method thereof.
The technical scheme of the invention is as follows: the preparation method of the high-strength hollow fiber ultrafiltration membrane comprises the following steps of:
step S1: preparing a casting solution: according to parts by weight, 24.5 parts of diethylene glycol is slowly added into 54 parts of dimethylacetamide, and 1, 10-phenanthroline modified ZIF-8, 1, 10-phenanthroline modified ZIF-8/Fe compound or 1, 10-phenanthroline modified ZIF-8/Fe/CeO are added at a stirring speed of 500r/min 2 Stirring one of the compounds for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under a nitrogen atmosphere at a stirring speed of 500r/min; and then naturally cooling to 30 ℃, and maintaining the vacuum defoaming at the temperature of 30 ℃ for one day to obtain the casting solution.
And S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
Further, 1, 10-phenanthroline modified ZIF-8 is added in the step S1, and the content of the 1, 10-phenanthroline modified ZIF-8 is 0.5 part.
Further, 1, 10-phenanthroline modified ZIF-8/Fe compound with the content of 0.5 part is added in the step S1.
Further, 1, 10-phenanthroline modified ZIF-8/Fe/CeO is added in the step S1 2 The content of the composition is 0.5-1 part.
Compared with the prior art, the invention has the beneficial effects that:
ZIF-8/Fe/CeO is modified by adding 1, 10-phenanthroline 2 The compound solves the problem that the entrapment rate of the hollow fiber ultrafiltration membrane to bovine serum albumin is too low when 1, 10-phenanthroline is used for modifying ZIF-8/Fe, and maintains the entrapment rate and higher pure water flux to the bovine serum albumin while improving the tensile strength.
Detailed Description
The present invention will be further illustrated by the following examples, which are given in parts by weight, unless otherwise specified.
The synthesis method of ZIF-8 in the invention comprises the following steps:
3.00g of zinc nitrate hexahydrate was dissolved in 50 mL methanol and then added to 100mL of a methanol solution containing 3.34g of 2-methylimidazole; the mixed solution was stirred for 12h, and the suspension was washed three times with methanol by centrifugation and then dried overnight in a vacuum oven at 60 ℃ to give ZIF-8.
The synthesis method of the 1, 10-phenanthroline modified ZIF-8 comprises the following steps:
dispersing 0.5g ZIF-8 and 0.125g 1, 10-phenanthroline in 45ml ethanol and distilled water solution with a volume ratio of 2:1, and magnetically stirring for 2 hours; vacuum drying at 80deg.C overnight; grinding the dried product into fine powder, carbonizing in a tube furnace with the heating rate of 5 ℃/min, and keeping the temperature of 900 ℃ for 3 hours under the protection of continuous argon; and then naturally cooling the sample to room temperature to obtain the 1, 10-phenanthroline modified ZIF-8.
The synthesis method of the 1, 10-phenanthroline modified ZIF-8/Fe compound comprises the following steps:
adding 100mg of ferrocene and 400mg of 1, 10-phenanthroline modified ZIF-8 into a tube furnace for carbonization, heating the center temperature of the furnace to 120 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 3 hours; then, the temperature is further increased to 900 ℃, and the pyrolysis is carried out at the speed of 5 ℃/min for 2 hours, and then, the mixture is naturally cooled to room temperature, so as to obtain the 1, 10-phenanthroline modified ZIF-8/Fe compound.
In the invention, 1, 10-phenanthroline is modified with ZIF-8/Fe/CeO 2 The synthesis method of the compound comprises the following steps:
80mg of 1, 10-phenanthroline modified ZIF-8/Fe complex and 30 mg of Ce (acac) 3 Dispersing in 10ml distilled water, sonicating for 30min, and lyophilizing overnight; then, the powder was subjected to low-temperature annealing treatment for 3 hours by heating to 120 ℃ (heating rate of 2 ℃/min) in an argon gas stream; then, the temperature is further increased to 900 ℃, and the heating rate is 5 ℃/min; then, naturally cooling the sample to room temperature; finally obtaining the 1, 10-phenanthroline modified ZIF-8/Fe/CeO 2 A complex.
The method for measuring the pure water flux in the invention comprises the following steps: adopting a pure water flux testing device for hollow fiber membrane wires in the prior art, pre-pressing the membrane wires for 30min under 0.1MPa, then testing the water yield volume to be V and the filtering area of the membrane wires to be S within the time t, wherein the purified water flux is J=V/St, wherein the V unit is L, the t unit is h and the S unit is m 2 . The average value of the flux of 5 different membrane filaments in the same batch is taken as the flux of the membrane filaments in the batch.
The method for measuring the bovine serum albumin retention rate is a method commonly used in the prior art, and specifically comprises the following steps:
firstly preparing a series of BSA solutions, measuring the absorbance of the series of BSA solutions at the wavelength of 280nm by using an ultraviolet-visible spectrophotometer, and then drawing a standard curve of the concentration and absorbance of BSA;
preparing a BSA solution of 1 g.L-1, pouring the BSA solution into a liquid tank of a self-made testing device (the testing device with the same pure water flux of hollow fiber membrane wires), fixing a membrane assembly on a tributary interface of the device, and then pre-pressing for 15 minutes under 0.1Mpa, and collecting filtrate. 5 samples were assayed, 3 times for each sample, and the average was taken.
The method for measuring the tensile strength comprises the following steps: the tensile strength of the films was measured using an electronic single fiber tester (LLY-06), and the films were weighed using a balance to obtain film yarn densities, a nip of 10mm, a stretching rate of 10mm/min, 3 measurements per group of samples, and an average value was obtained.
Example 1
Step S1: preparing a casting solution: slowly adding 24.5 parts of diethylene glycol into 54 parts of dimethylacetamide, adding 0.5 part of ZIF-8 at a stirring speed of 500r/min, stirring for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under a nitrogen atmosphere, wherein the stirring speed is 500r/min; and then naturally cooling to 30 ℃, and maintaining the vacuum defoaming at the temperature of 30 ℃ for one day to obtain the casting solution.
And S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
Performance test is carried out on the hollow fiber ultrafiltration membrane, the tensile strength of the hollow fiber ultrafiltration membrane is 17Mpa at room temperature, and the pure water flux of the hollow fiber ultrafiltration membrane is 1323L/m at 0.1Mpa 2 h, the retention rate of bovine serum albumin is 92%.
Example 2
Step S1: preparing a casting solution: slowly adding 24.5 parts of diethylene glycol into 54 parts of dimethylacetamide, adding 0.5 part of 1, 10-phenanthroline modified ZIF-8 at a stirring speed of 500r/min, stirring for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under a nitrogen atmosphere at a stirring speed of 500r/min; and then naturally cooling to 30 ℃, and maintaining the vacuum defoaming at the temperature of 30 ℃ for one day to obtain the casting solution.
And S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
Performance test is carried out on the hollow fiber ultrafiltration membrane, the tensile strength of the hollow fiber ultrafiltration membrane is 23Mpa at room temperature, and the hollow fiber is 0.1MpaThe pure water flux of the Ultrafiltration membrane is 1357L/m 2 h, the retention rate of bovine serum albumin is 81%.
Example 3
Step S1: preparing a casting solution: slowly adding 24.5 parts of diethylene glycol into 54 parts of dimethylacetamide, adding 0.5 part of 1, 10-phenanthroline modified ZIF-8/Fe compound at a stirring speed of 500r/min, stirring for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under a nitrogen atmosphere at a stirring speed of 500r/min; and then naturally cooling to 30 ℃, and maintaining the vacuum defoaming at the temperature of 30 ℃ for one day to obtain the casting solution.
And S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
Performance test is carried out on the hollow fiber ultrafiltration membrane, the tensile strength of the hollow fiber ultrafiltration membrane is 35Mpa at room temperature, and the pure water flux of the hollow fiber ultrafiltration membrane is 1342L/m at 0.1MPa 2 h, the entrapment rate of bovine serum albumin is 60%.
Example 4
Step S1: preparing a casting solution: adding 24.5 parts of diethylene glycol into 54 parts of dimethylacetamide slowly, and adding 0.5 part of 1, 10-phenanthroline modified ZIF-8/Fe/CeO at a stirring speed of 500r/min 2 Stirring the compound for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under nitrogen atmosphere at the stirring speed of 500r/min; and then naturally cooling to 30 ℃, and maintaining the vacuum defoaming at the temperature of 30 ℃ for one day to obtain the casting solution.
And S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
Performance test is carried out on the hollow fiber ultrafiltration membrane, the tensile strength of the hollow fiber ultrafiltration membrane is 32Mpa at room temperature, and the hollow fiber is 0.1MpaThe pure water flux of the Ultrafiltration membrane is 1357L/m 2 h, the retention rate of bovine serum albumin is 88%.
Example 5
Step S1: preparing a casting solution: adding 24.5 parts of diethylene glycol into 54 parts of dimethylacetamide slowly, and adding 0.7 part of 1, 10-phenanthroline modified ZIF-8/Fe/CeO at a stirring speed of 500r/min 2 Stirring the compound for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under nitrogen atmosphere at the stirring speed of 500r/min; and then naturally cooling to 30 ℃, and maintaining the vacuum defoaming at the temperature of 30 ℃ for one day to obtain the casting solution.
And S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
Performance test is carried out on the hollow fiber ultrafiltration membrane, the tensile strength of the hollow fiber ultrafiltration membrane is 36Mpa at room temperature, and the pure water flux of the hollow fiber ultrafiltration membrane is 1270L/m at 0.1MPa 2 h, the retention rate of bovine serum albumin is 87%.
Example 6
Step S1: preparing a casting solution: 24.5 parts of diethylene glycol is slowly added into 54 parts of dimethylacetamide, and 1 part of 1, 10-phenanthroline modified ZIF-8/Fe/CeO is added at the stirring speed of 500r/min 2 Stirring the compound for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under nitrogen atmosphere at the stirring speed of 500r/min; and then naturally cooling to 30 ℃, and maintaining the vacuum defoaming at the temperature of 30 ℃ for one day to obtain the casting solution.
And S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
Performance test was conducted on the hollow fiber ultrafiltration membrane having a tensile strength of 35Mpa at room temperature at 0.1MThe pure water flux of the hollow fiber ultrafiltration membrane under Pa is 812L/m 2 h, the retention rate of bovine serum albumin is 86%.
From the test data, 1, 10-phenanthroline modified ZIF-8/Fe/CeO 2 The addition of (2) increases the tensile strength of the hollow fiber membrane, but affects the pure water flux, and the content thereof needs to be strictly controlled.
The above embodiments are only preferred embodiments of the present invention and are not intended to limit the scope of the present invention, so that all equivalent changes or modifications made according to the principles of the present invention as set forth in the appended claims shall fall within the scope of the present invention.
Claims (7)
1. A high-strength hollow fiber ultrafiltration membrane is characterized in that,
the preparation method of the high-strength hollow fiber ultrafiltration membrane comprises the following steps:
step S1: preparing a casting solution: according to parts by weight, 24.5 parts of diethylene glycol is slowly added into 54 parts of dimethylacetamide, and 1, 10-phenanthroline modified ZIF-8, 1, 10-phenanthroline modified ZIF-8/Fe compound or 1, 10-phenanthroline modified ZIF-8/Fe/CeO are added at a stirring speed of 500r/min 2 Stirring one of the compounds for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under a nitrogen atmosphere at a stirring speed of 500r/min; naturally cooling to 30 ℃, and maintaining the vacuum defoamation at the temperature of 30 ℃ for one day to obtain casting film liquid;
and S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining the casting solution in air for 2-3S, directly entering a solidification water bath at 30 ℃, soaking the casting solution in 1.0M sulfuric acid for 2h, continuously cleaning the casting solution in pure water, respectively soaking the casting solution in methanol and n-hexane, and drying the casting solution at 60 ℃.
2. The high-strength hollow fiber ultrafiltration membrane according to claim 1, wherein 1, 10-phenanthroline modified ZIF-8 is added in the step S1, and the content thereof is 0.5 part by weight.
3. The high-strength hollow fiber ultrafiltration membrane according to claim 1, wherein 1, 10-phenanthroline modified ZIF-8/Fe compound is added in the step S1, and the content of the 1, 10-phenanthroline modified ZIF-8/Fe compound is 0.5 part by weight.
4. The high-strength hollow fiber ultrafiltration membrane according to claim 1, wherein 1, 10-phenanthroline modified ZIF-8/Fe/CeO is added in the step S1 2 The compound is 0.5-1 part by weight.
5. The high-strength hollow fiber ultrafiltration membrane according to claim 4, wherein 1, 10-phenanthroline modified ZIF-8/Fe/CeO is added in the step S1 2 The compound contains 0.7-1 part by weight.
6. The high-strength hollow fiber ultrafiltration membrane according to claim 4, wherein 1, 10-phenanthroline modified ZIF-8/Fe/CeO is added in the step S1 2 The compound content was 0.7 parts by weight.
7. The preparation method of the high-strength hollow fiber ultrafiltration membrane is characterized by comprising the following steps of:
step S1: preparing a casting solution: according to parts by weight, 24.5 parts of diethylene glycol is slowly added into 54 parts of dimethylacetamide, and 0.7 part of 1, 10-phenanthroline modified ZIF-8/Fe/CeO is added under the stirring speed of 500r/min 2 Stirring the compound for 1 hour, adding 18 parts of polyethersulfone, continuously stirring and heating to 80 ℃, and stirring for 24 hours under nitrogen atmosphere at the stirring speed of 500r/min; naturally cooling to 30 ℃, and maintaining the vacuum defoamation at the temperature of 30 ℃ for one day to obtain casting film liquid;
step S2, passing the casting solution through a spinning nozzle grinding tool under the pressure of 0.4Mpa, maintaining in air for 2-3S, directly entering a 30 ℃ coagulating water bath, then soaking in 1.0M sulfuric acid for 2h, then continuing to clean in pure water, then respectively soaking in methanol and n-hexane, and then drying at 60 ℃;
the 1, 10-phenanthroline modified ZIF-8/Fe/CeO 2 The preparation method of the compound comprises the following steps: modifying 80mg of 1, 10-phenanthrolineZIF-8/Fe complex and Ce (acac) of 30 mg 3 Dispersing in 10ml distilled water, sonicating for 30min, and lyophilizing overnight; then, heating the powder to 120 ℃ in argon flow, wherein the heating rate is 2 ℃/min, and carrying out low-temperature annealing treatment for 3 hours; then, the temperature is further increased to 900 ℃, and the heating rate is 5 ℃/min; then, naturally cooling the sample to room temperature; finally obtaining the 1, 10-phenanthroline modified ZIF-8/Fe/CeO 2 A complex.
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