CN118267865A - Preparation method of PES ultrafiltration membrane - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 56
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 60
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims abstract description 24
- 238000005266 casting Methods 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 10
- IJJLRUSZMLMXCN-SLPGGIOYSA-N (2r,3r,4s,5r)-2,3,4,6-tetrahydroxy-5-sulfanylhexanal Chemical compound OC[C@@H](S)[C@@H](O)[C@H](O)[C@@H](O)C=O IJJLRUSZMLMXCN-SLPGGIOYSA-N 0.000 claims abstract description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007790 scraping Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 23
- 239000012621 metal-organic framework Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- GGQRKYMKYMRZTF-UHFFFAOYSA-N 2,2,3,3-tetrakis(prop-1-enyl)butanedioic acid Chemical compound CC=CC(C=CC)(C(O)=O)C(C=CC)(C=CC)C(O)=O GGQRKYMKYMRZTF-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000004907 flux Effects 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002070 nanowire Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002307 Dextran Polymers 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 238000006664 bond formation reaction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 zirconium ions Chemical class 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a PES ultrafiltration membrane, which relates to the technical field of PES ultrafiltration membrane preparation, wherein polyether sulfone is placed in a radio frequency plasma generator and treated by using mixed gas of hydrogen and nitrogen to obtain polyether sulfone with amino; weighing 10-15 parts of polyether sulfone with amino group, 4-8 parts of precursor of propenyl metal organic frame material, 0.02-0.2 part of 5-thio-D-glucose, 100-150 parts of N, N-dimethylacetamide, 1-5 parts of polyvinylpyrrolidone and 1-3 parts of diethanolamine, stirring in a reaction kettle at 50-60 ℃ for 2-4 hours, pouring casting solution on a glass plate after defoaming, and scraping the casting solution into a film by using an automatic film coater to obtain a PES (polyether sulfone) ultrafiltration membrane with better separability; the flux recovery rate is 96.83%, and the pollution resistance is good.
Description
Technical Field
The invention relates to the technical field of PES ultrafiltration membrane preparation, in particular to a preparation method of a PES ultrafiltration membrane.
Background
As one of the most commonly used polymer membranes in industrial production, the polyether sulfone (PES) membrane has the advantages of good mechanical property, chemical cleaning resistance, corrosion resistance, high temperature resistance and the like, and can rapidly, efficiently and pertinently remove protein, bacteria and viruses in water and even soluble salts and organic matters with smaller particle size by regulating the pore size of the membrane, thereby having wide and deep application in a plurality of fields such as sea water desalination, wastewater treatment, drinking water purification and the like.
Chinese patent CN107441936a: a mixed Ag-TiO 2/SPES ultrafiltration membrane is disclosed, which is prepared by blending a certain amount of Ag-TiO 2 nano particles into sulfonated polyether sulfone casting solution and then converting the mixture into a membrane by a solvent-phase non-solvent phase method. Also discloses a preparation method and application of the Ag-TiO 2/SPES mixed ultrafiltration membrane.
Chinese patent CN107551828a: discloses a PES-TiO 2 nanowire blend ultrafiltration membrane, wherein a certain amount of TiO 2 nanowires are uniformly dispersed in the PES ultrafiltration membrane; the preparation process of the PES-TiO 2 nanowire blended ultrafilter film is also disclosed, and the required amount of TiO 2 nanowire is added into polyether sulfone casting solution and then converted into film through solvent-phase non-solvent phase method. Finally, the application of the PES-TiO 2 nanowire blending ultrafiltration membrane in separating and filtering humic acid organic molecules is disclosed.
Chinese patent CN107376673B: the PES ultrafiltration membrane loaded with TiO 2 nanotubes is disclosed, a certain amount of TiO 2 nanotubes are loaded on the surface of the PES ultrafiltration membrane, and the TiO 2 nanotubes are grafted on the surface of the PES ultrafiltration membrane through dopamine and organosilane coupling agents. Also discloses a preparation method and application of the PES ultrafiltration membrane loaded with the TiO 2 nanotube.
The ultrafiltration membrane prepared by the above patent and the prior art cannot effectively intercept required substances, cannot effectively improve the anti-pollution capability, and can leak particles in the membrane after long-term use in various environments, and secondary pollution is caused while the performance is reduced.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a PES ultrafiltration membrane, which comprises the following operation steps:
H1: the method comprises the steps of placing polyethersulfone in a radio frequency plasma generator, and treating by using a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the mixed gas is as follows: nitrogen=1:2-4, treatment time is 30-60 seconds, and polyether sulfone with amino is obtained;
h2: weighing 10-15 parts by weight of polyether sulfone with amino group, 4-8 parts by weight of precursor of propenyl metal organic frame material, 0.02-0.2 part by weight of 5-thio-D-glucose, 100-150 parts by weight of N, N-dimethylacetamide, 1-5 parts by weight of polyvinylpyrrolidone and 1-3 parts by weight of diethanolamine, stirring in a reaction kettle at 50-60 ℃ for 2-4 hours, stirring at normal temperature for 10-15 hours, and then putting into an ultrasonic cleaner for defoaming;
and H3: after defoaming, pouring the casting solution on a glass plate, scraping the casting solution into a film by using an automatic film coater, putting the glass plate coated with the casting solution into deionized water smoothly, performing phase conversion into a film, and standing for 20-25h to obtain the PES ultrafiltration membrane.
Preferably, the power of the H1 radio frequency plasma generator is 50-100W, and the working pressure is 0.1-1Torr.
Preferably, the flow rate of the mixed gas of the hydrogen and the nitrogen of the H1 is 10-20ml/min.
Preferably, the deaeration time of the H2 is 4-7H.
Preferably, the preparation method of the precursor of the H2 propenyl metal organic framework material comprises the following steps:
S1: weighing 20-25 parts by weight of zirconium tetrachloride, 15-20 parts by weight of tetrapropenyl succinic acid, 15-20 parts by weight of polyvinylpyrrolidone and 200-300 parts by weight of dimethylformamide, and uniformly mixing;
S2: pouring the solution prepared in the step S1 into a reaction kettle for reaction; after the reaction is finished, the dimethylformamide is distilled off, and the precursor of the propenyl metal organic framework material is obtained.
Further, in the step S2, the reaction temperature is 140-160 ℃ and the reaction time is 8-12h.
Preferably, the H3 film has a thickness of 150-250 μm.
The preparation mechanism of the precursor of the propenyl metal organic framework material comprises the following steps:
The amino group (serving as a nucleophile) on the polyether sulfone with the amino group and the propenyl group (serving as an electrophile) in the propenyl metal organic framework material precursor undergo Michael addition reaction; this reaction is a carbon-nitrogen bond formation process, which is carried out under alkaline conditions, where diethanolamine plays a role in promoting the reaction;
The sulfhydryl in the 5-thio-D-glucose and the propenyl group of the precursor of the propenyl metal organic framework material undergo Michael addition reaction; this is a highly efficient carbon-sulfur bond formation reaction, yielding grafted zirconium complexes;
the metal organic framework precursor grafted to polyethersulfone further forms a stable coordination bond with zirconium ions, thereby obtaining the ultrafiltration membrane with specific pore diameter and chemical property.
Compared with the prior art, the preparation method of the PES ultrafiltration membrane has the following remarkable effects:
1. High rejection rate:
The PES ultrafiltration membrane prepared has high glucan retention rate of 94.51%, which shows that the PES ultrafiltration membrane has excellent separation performance, can effectively retain macromolecular substances, and is suitable for separation processes requiring high resolution;
2. good flux recovery:
the flux recovery rate reaches 96.83%, which shows that the ultrafiltration membrane can be recovered to be close to the original flux through simple cleaning after being polluted, and the ultrafiltration membrane has good anti-pollution capability and long-term use stability;
3. improved resistance to contamination:
Because the membrane surface is grafted with a specific organic frame material, the adsorption and deposition of pollutants on the membrane surface can be reduced, so that the anti-pollution capability of the membrane is improved, and the cleaning frequency and the maintenance cost are reduced.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the intended purpose of the present invention, the following detailed description will refer to the specific implementation, structure, characteristics and effects according to the present invention in conjunction with the preferred embodiments.
The instrument used in the invention comprises: TSD502 type gel permeation chromatography (Markov instruments Co., ltd., UK) equipped with differential refraction and multi-angle laser detector, TSKGelG PWXL chromatographic column, mobile phase of acetic acid solution of 0.1mol/L, sample test flow rate of 1.0mL/min, sample cell detection temperature of 30deg.C; ultrafiltration membrane component testing device (developed by national research institute for sea water desalination and comprehensive utilization); WGZ-800 type turbidity meter (Shanghai san family Instrument works).
1. Rejection rate:
A dextran solution with the concentration of 1000mg/L is prepared, ultrafiltration is performed for 30min at room temperature under the condition that the water inlet pressure is 0.3MP, and the retention rate R= (1-Cp/Cf) x100% of PES is tested, wherein Cp is the concentration of dextran in the filtrate, and Cf is the concentration of dextran in the raw material solution.
2. Resistance to contamination:
After the membrane is put into a membrane tank, pure water is introduced into the membrane tank for prepressing for 30min, and then the pure water flux is measured for 1 time every 10min [ J 1,L/(m2. H ], and the measurement is carried out for 30min. The pure water was then replaced with BSA solution having a mass concentration of 1g/L as a simulated contaminant, again measured 1 time every 10 minutes for 30 minutes. Then washing the ultrafiltration membrane with deionized water for 30min, and after washing, changing into deionized water to measure the recovered water flux [ J 2,L/(m2. H ] after washing, measuring 1 time every 10min, and measuring 30min; the experiments were performed 3 times in parallel, and the calculated average value of 3 groups of similar data was taken as the final flux recovery rate. Flux recovery frr=j 2/J1 ×100%, where J 1、J2 is the membrane pure water flux before and after contamination, L/(m 2 ·h), respectively.
Example 1
A preparation method of a PES ultrafiltration membrane comprises the following operation steps:
h1: the method comprises the steps of placing polyethersulfone in a radio frequency plasma generator, and treating by using a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the mixed gas is as follows: nitrogen=1:2, treatment time of 30 seconds, giving polyether sulfone with amino groups;
H2: 10g of polyether sulfone with amino group, 4g of precursor of propenyl metal organic framework material, 0.02g of 5-thio-D-glucose, 100g of N, N-dimethylacetamide, 1g of polyvinylpyrrolidone and 1g of diethanolamine are weighed, stirred in a reaction kettle for 2 hours at 50 ℃, stirred for 10 hours at normal temperature, and then put in an ultrasonic cleaner for defoaming the solution;
and H3: after defoaming, pouring the casting solution on a glass plate, scraping the casting solution into a film by using an automatic film coater, putting the glass plate coated with the casting solution into deionized water smoothly, performing phase conversion into a film, and standing for 20h to obtain the PES ultrafiltration membrane.
The power of the H1 radio frequency plasma generator is 50W, and the working pressure is 0.1Torr.
The flow rate of the mixed gas of the hydrogen and the nitrogen of the H1 is 10ml/min.
The defoaming time of the H2 is 4H.
The preparation method of the precursor of the H2 propenyl metal organic framework material comprises the following steps:
S1: weighing 20g of zirconium tetrachloride, 15g of tetrapropenyl succinic acid, 15g of polyvinylpyrrolidone and 200g of dimethylformamide, and uniformly mixing;
S2: pouring the solution prepared in the step S1 into a reaction kettle for reaction; after the reaction is finished, the dimethylformamide is distilled off, and the precursor of the propenyl metal organic framework material is obtained.
The reaction temperature of S2 is 140 ℃ and the reaction time is 8h.
The thickness of the H3 film is 150 μm.
Example 2
A preparation method of a PES ultrafiltration membrane comprises the following operation steps:
H1: the method comprises the steps of placing polyethersulfone in a radio frequency plasma generator, and treating by using a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the mixed gas is as follows: nitrogen=1:3, treatment time 40 seconds, giving polyether sulfone with amino groups;
H2: weighing 12g of polyether sulfone with amino group, 5g of precursor of propenyl metal organic framework material, 0.1g of 5-thio-D-glucose, 110g of N, N-dimethylacetamide, 2g of polyvinylpyrrolidone and 2g of diethanolamine, stirring in a reaction kettle at 55 ℃ for 3 hours, stirring at normal temperature for 12 hours, and then putting into an ultrasonic cleaner to defoam the solution;
And H3: after defoaming, pouring the casting solution on a glass plate, scraping the casting solution into a film by using an automatic film coater, putting the glass plate coated with the casting solution into deionized water smoothly, performing phase conversion into a film, and standing for 22h to obtain the PES ultrafiltration membrane.
The power of the H1 radio frequency plasma generator is 60W, and the working pressure is 0.5Torr.
The flow rate of the mixed gas of the hydrogen and the nitrogen of the H1 is 15ml/min.
The defoaming time of the H2 is 5H.
The preparation method of the precursor of the H2 propenyl metal organic framework material comprises the following steps:
s1: weighing 22g of zirconium tetrachloride, 16g of tetrapropenyl succinic acid, 16g of polyvinylpyrrolidone and 240g of dimethylformamide, and uniformly mixing;
S2: pouring the solution prepared in the step S1 into a reaction kettle for reaction; after the reaction is finished, the dimethylformamide is distilled off, and the precursor of the propenyl metal organic framework material is obtained.
The reaction temperature of S2 is 145 ℃ and the reaction time is 9h.
The thickness of the H3 film was 200. Mu.m.
Example 3
A preparation method of a PES ultrafiltration membrane comprises the following operation steps:
H1: the method comprises the steps of placing polyethersulfone in a radio frequency plasma generator, and treating by using a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the mixed gas is as follows: nitrogen=1:3, treatment time of 50 seconds, giving polyether sulfone with amino groups;
H2: 14g of polyether sulfone with amino group, 7g of precursor of propenyl metal organic framework material, 0.15g of 5-thio-D-glucose, 140g of N, N-dimethylacetamide, 4g of polyvinylpyrrolidone and 2g of diethanolamine are weighed, stirred in a reaction kettle for 3 hours at 55 ℃, stirred for 14 hours at normal temperature, and then put in an ultrasonic cleaner for defoaming the solution;
and H3: after defoaming, pouring the casting solution on a glass plate, scraping the casting solution into a film by using an automatic film coater, putting the glass plate coated with the casting solution into deionized water smoothly, performing phase conversion into a film, and standing for 24 hours to obtain the PES ultrafiltration membrane.
The power of the H1 radio frequency plasma generator is 90W, and the working pressure is 0.8Torr.
The flow rate of the mixed gas of the hydrogen and the nitrogen of the H1 is 15ml/min.
The defoaming time of the H2 is 6H.
The preparation method of the precursor of the H2 propenyl metal organic framework material comprises the following steps:
s1: weighing 24g of zirconium tetrachloride, 18g of tetrapropenyl succinic acid, 18g of polyvinylpyrrolidone and 280g of dimethylformamide, and uniformly mixing;
S2: pouring the solution prepared in the step S1 into a reaction kettle for reaction; after the reaction is finished, the dimethylformamide is distilled off, and the precursor of the propenyl metal organic framework material is obtained.
The reaction temperature of S2 is 155 ℃ and the time is 11h.
The thickness of the H3 film was 200. Mu.m.
Example 4
A preparation method of a PES ultrafiltration membrane comprises the following operation steps:
H1: the method comprises the steps of placing polyethersulfone in a radio frequency plasma generator, and treating by using a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the mixed gas is as follows: nitrogen=1:4, treatment time of 60 seconds, giving polyether sulfone with amino groups;
H2: 15g of polyether sulfone with amino group, 8g of precursor of propenyl metal organic framework material, 0.2g of 5-thio-D-glucose, 150g of N, N-dimethylacetamide, 5g of polyvinylpyrrolidone and 3g of diethanolamine are weighed, stirred in a reaction kettle for 4 hours at 60 ℃, stirred for 15 hours at normal temperature, and then put in an ultrasonic cleaner for defoaming the solution;
And H3: after defoaming, pouring the casting solution on a glass plate, scraping the casting solution into a film by using an automatic film coater, putting the glass plate coated with the casting solution into deionized water smoothly, performing phase conversion into a film, and standing for 25 hours to obtain the PES ultrafiltration membrane.
The power of the H1 radio frequency plasma generator is 100W, and the working pressure is 1Torr.
The flow rate of the mixed gas of the hydrogen and the nitrogen of the H1 is 20ml/min.
The defoaming time of the H2 is 7H.
The preparation method of the precursor of the H2 propenyl metal organic framework material comprises the following steps:
S1: weighing 25g of zirconium tetrachloride, 20g of tetrapropenyl succinic acid, 20g of polyvinylpyrrolidone and 300g of dimethylformamide, and uniformly mixing;
S2: pouring the solution prepared in the step S1 into a reaction kettle for reaction; after the reaction is finished, the dimethylformamide is distilled off, and the precursor of the propenyl metal organic framework material is obtained.
The reaction temperature of S2 is 160 ℃ and the reaction time is 12h.
The thickness of the H3 film is 250 μm.
Comparative example 1
The procedure of example 1 was repeated except that the precursor of the acryl-based metal-organic framework material was not added.
Comparative example 2
The procedure of example 1 was repeated except that the aminopolyether sulfone was not added.
Comparative example 3
5-Thio-D-glucose was not added, otherwise as in example 1.
Test results for the above embodiments:
| Rejection/% | Flux recovery/% | |
| Example 1 | 93.06 | 95.32 |
| Example 2 | 93.67 | 95.75 |
| Example 3 | 94.12 | 96.37 |
| Example 4 | 94.51 | 96.83 |
| Comparative example 1 | 78.31 | 80.79 |
| Comparative example 2 | 83.45 | 86.25 |
| Comparative example 3 | 86.12 | 89.36 |
Through the data analysis of the above examples and comparative examples, the PES ultrafiltration membrane prepared by the invention has high rejection rate and good flux recovery rate, which shows that the ultrafiltration membrane can be recovered to be close to the original flux through simple cleaning after being polluted, and shows good anti-pollution capability and long-term use stability.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (7)
1. A preparation method of a PES ultrafiltration membrane comprises the following operation steps:
H1: the method comprises the steps of placing polyethersulfone in a radio frequency plasma generator, and treating by using a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the mixed gas is as follows: nitrogen=1, (2-4), treatment time is 30-60 seconds, and polyether sulfone with amino is obtained;
h2: weighing 10-15 parts by weight of polyether sulfone with amino group, 4-8 parts by weight of precursor of propenyl metal organic frame material, 0.02-0.2 part by weight of 5-thio-D-glucose, 100-150 parts by weight of N, N-dimethylacetamide, 1-5 parts by weight of polyvinylpyrrolidone and 1-3 parts by weight of diethanolamine, stirring in a reaction kettle at 50-60 ℃ for 2-4 hours, stirring at normal temperature for 10-15 hours, and then putting into an ultrasonic cleaner for defoaming;
and H3: after defoaming, pouring the casting solution on a glass plate, scraping the casting solution into a film by using an automatic film coater, putting the glass plate coated with the casting solution into deionized water smoothly, performing phase conversion into a film, and standing for 20-25h to obtain the PES ultrafiltration membrane.
2. The method for preparing the PES ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: in the H1, the power of the radio frequency plasma generator is 50-100W, and the working pressure is 0.1-1Torr.
3. The method for preparing the PES ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: in the H1, the flow rate of the mixed gas of the hydrogen and the nitrogen is 10-20ml/min.
4. The method for preparing the PES ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: in the H2, the defoaming time is 4-7H.
5. The method for preparing the PES ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: in the H2, the preparation method of the precursor of the propenyl metal organic framework material comprises the following steps:
S1: weighing 20-25 parts by weight of zirconium tetrachloride, 15-20 parts by weight of tetrapropenyl succinic acid, 15-20 parts by weight of polyvinylpyrrolidone and 200-300 parts by weight of dimethylformamide, and uniformly mixing;
S2: pouring the solution prepared in the step S1 into a reaction kettle for reaction; after the reaction is finished, the dimethylformamide is distilled off, and the precursor of the propenyl metal organic framework material is obtained.
6. The method for preparing the PES ultrafiltration membrane according to claim 5, wherein the method comprises the following steps: in the step S2, the reaction temperature is 140-160 ℃ and the reaction time is 8-12h.
7. The method for preparing the PES ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: in the H3, the film thickness is 150-250 μm.
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