CN103127847B - Anti-protein-pollution polyacrylonitrile hydrolyzed modified ultra-filtration membrane and preparation method thereof - Google Patents
Anti-protein-pollution polyacrylonitrile hydrolyzed modified ultra-filtration membrane and preparation method thereof Download PDFInfo
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 46
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 17
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 210000002469 basement membrane Anatomy 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- DHXNZYCXMFBMHE-UHFFFAOYSA-N 3-bromopropanoic acid Chemical compound OC(=O)CCBr DHXNZYCXMFBMHE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 claims description 4
- 241001044369 Amphion Species 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- QRMLKVVWCJUMPR-UHFFFAOYSA-N BrCC[Na] Chemical compound BrCC[Na] QRMLKVVWCJUMPR-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000008053 sultones Chemical class 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 23
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 210000004379 membrane Anatomy 0.000 description 14
- 230000003373 anti-fouling effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000009285 membrane fouling Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000372132 Hydrometridae Species 0.000 description 1
- DRPNQFVBFKYFAY-UHFFFAOYSA-N S(=O)(C1=CC=C(C=C1)N)(=O)N.C(C=C)#N Chemical compound S(=O)(C1=CC=C(C=C1)N)(=O)N.C(C=C)#N DRPNQFVBFKYFAY-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention discloses an anti-protein-pollution polyacrylonitrile hydrolyzed modified ultra-filtration membrane and a preparation method of the anti-protein-pollution polyacrylonitrile hydrolyzed modified ultra-filtration membrane. The anti-protein-pollution polyacrylonitrile hydrolyzed modified ultra-filtration membrane is prepared by hydrolyzing and grafting a polyacrylonitrile based membrane with amphoteric ions. The ultra-filtration membrane disclosed by the invention has very good anti-protein-pollution capability on protein molecules; a membrane preparation process is simple and conditions are moderate; and after the polyacrylonitrile ultra-filtration membrane is hydrolyzed and modified, the anti-pollution resistance of the membrane is obviously improved under the precondition of guaranteeing the high flux and the retention rate of the membrane.
Description
Technical field
The present invention relates to a kind of polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution method, belong to ultrafiltration membrane surface modification technology.
Background technology
Ultrafiltration is the liquid phases separation that separating medium carries out based on screening mechanism with film under the effect of differential static pressure motive force, and the main separate object of milipore filter is protein, various enzyme, bacterium, virus, latex etc.Ultrafiltration, as a kind of new and effective isolation technics, has some obvious advantages: without phase transformation, can be separated under normal temperature and low pressure, can the physiologically active of Protein requirement very well; Energy consumption is low, and equipment volume is little, and structure is simple; Technological adaptability is strong, is easy to Automated condtrol etc.At present, hyperfiltration technique has been widely used in ultra-pure water preparation, electrophoretic paint reclaims and the aspect such as other wastewater treatments, dairy products processing and beverage is refined, the concentrating and separating of enzyme and biological products.
Present stage, the main cause of restriction hyperfiltration technique large-scale application efficiency is membrane pollution problem, and the large biological molecule in ie in solution is adsorbed on film surface, causes the reduction in Pore Blocking and aperture, cause the continuous decrease of ultrafiltration performance, have a strong impact on the economy of hyperfiltration technique.Carry out research from molecular scale to the antifouling property of membrane material to find: the performance that the hydrophilic radicals such as amphion group have obvious CKIs matter to adsorb.
In conventional membrane material, polyacrylonitrile (PAN) has very excellent light resistance, fungus resistance and reasonable solvent resistance, chemical stability and heat endurance, is thus widely applied.But at present also to there is hydrophily poor and can run into the problems such as more serious fouling membrane in protein solution separation process for PAN film.So the chemical modification be suitable for polyacrylonitrile basement membrane is the effective way improving its separative efficiency, extend its service life.Research finds, carries out graft modification can effectively improve its antifouling property to polyacrylonitrile hydrolyzed film.Membrane surface modification requires general to increase film surface hydrophilicity according to the literature, finds that there is two class materials possess excellent antifouling property through research: a class is the polymer such as material such as phosphatide, sulfanilamide (SN), sulfonic acid with amphion group; Another kind of is polyoxyethylene (PEO) or polyethylene glycol (PEG) etc.CN 101003003A is with acrylonitrile-methacylate dimethylamine ethyl ester and 1,3-N-morpholinopropanesulfonic acid lactone reaction is prepared acrylonitrile-sulfanilamide (SN) both sexes base polymer and is added masking in polyacrylonitrile to, introduce sulfanilamide (SN) group in acrylonitril membrane material after, while the hydrophily enhancing of film, the anti-protein-contamination ability of film significantly strengthens, and obtained film has good effect to separation condensing protein.The PluronicF127 that polyethers alum (PES) and molecular weight are 12600 is raw material by CN 101259387A, and the antifouling property of obtained polyethers alum milipore filter is improved largely, and has simultaneously good retain characteristic to protein.By regulating the mass percent adding additive, on the basis keeping antifouling property, obtaining a series of flux is the antipollution milipore filter that line style increases.But this modified material is directly joined masking in membrane material, to the structure of film, there is certain shadow.
Summary of the invention
The object of the present invention is to provide a kind of antipollution polyacrylonitrile hydrolyzed modified ultrafiltration membrane and preparation method thereof, the method activation process is comparatively simple, the active group number generated is also more, and the milipore filter prepared in this approach, has fabulous contamination resistance to protein molecule.
A kind of polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution provided by the invention, it is characterized in that by comprising the steps to make in interior method: by polyacrylonitrile basement membrane, be immersed in 0.5-1.5 h in the aqueous slkali of 50-70 DEG C, washing, and then be immersed in EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride) cushioning liquid in activate, activated hydrolysis film is at room temperature immersed in 20 more than h in 3-dimethylamino propylamine solution, film water is immersed in after washing in 40-60 DEG C of quaternary ammonium reagent and reacts 20 more than h, polyacrylonitrile amphion graft modification milipore filter is obtained through post processing.
In a preferred embodiment of the present invention, described quaternary ammonium reagent is selected from halogenosulfonic acid salt, halogenated acid, sultones; Preferably, described quaternary ammonium reagent is selected from the one in 3-bromo-propionic acid, 2-bromoethyl sodium sulfonate, PS.
A kind of polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution preparation method provided by the invention, comprises the following steps:
1) polyacrylonitrile ultrafiltration film basement membrane is immersed in the NaOH of 50-70 DEG C of 1-2 mol/L or KOH solution and takes out after 1 h-3 h, with alkali lye residual in rinsed with deionized water film.Its reaction equation is as follows:
2) made for step 1) hydrolysis film is immersed in the cushioning liquid of EDC activates 4 h-8 h, then use washed with de-ionized water 2-4 time.
3) by step 2) made polyacrylonitrile activation hydrolysis film is immersed in the 3-dimethylamino propylamine solution of 1 g/L-10 g/L and reacts 12 h-48 h, then uses washed with de-ionized water three times.Its reaction equation is as follows:
4) polyacrylonitrile film made for top is immersed in 50 DEG C of 3-bromo-propionic acid solution and reacts 12 h-48 h, film is taken out, after rinsed with deionized water 3 times, obtains polyacrylonitrile hydrolyzed modified ultrafiltration membrane.Its reaction equation is as follows:
Carry out dynamic filtration experiment to film and calculate relevant parameter, concrete steps are as follows:
Pure water flux is tested: first by film precompressed 30min under 0.14 MPa, measure the pure water flux J of film after flux stabilized under 0.1 MPa
w1.
J
w1for milipore filter flux (L/ m
2h), V is
time, A was the effective area (m of film through the volume (L) of water
2),
represent the time (h).
BSA(bovine serum albumin(BSA)) solution flux and film rejection test: configuration concentration 1 mg/ml BSA PBS, measures BSA solution flux J under 0.1 MPa
pand film is to the rejection R of BSA.
J in formula
pfor BSA solution flux (L/ m
2h), V
pfor through BSA liquor capacity (L), t is the testing time (h).
C in formula
fand C
pbe respectively BSA concentration in feed side and per-meate side solution, test with ultra-violet and visible spectrophotometer.
Flux recovery rate is tested: BSA solution is changed into clear water and is poured out by water after stirring and washing 0.5 h at ambient pressure, rejoin the pure water flux that deionized water measures film under 0.1MPa, be denoted as J
w2.
By the flux recovery rate of film
be denoted as, carry out the antifouling property of reaction film.
Usually the fouling membrane that can be removed by water-washing process is referred to as reversible membrane fouling; And remaining not removable part is referred to as irreversible membrane fouling, therefore in order to the anti pollution property of evaluated for film, introduce gross contamination index Rt, reversible membrane fouling index Rr, and irreversible membrane fouling index Rir.The antifouling property of milipore filter is compared by these three pollution indexs.
Gross contamination index Rt
Reversible membrane fouling index Rr
Irreversible membrane fouling index Rir
The invention has the advantages that: film preparation process is easy, mild condition, be hydrolyzed modified to polyacrylonitrile ultrafiltration membranes, under the prerequisite ensureing film higher flux and rejection, the antifouling property of film have also been obtained and significantly improves.
Detailed description of the invention
Embodiment 1
Polyacrylonitrile basement membrane is immersed in the NaOH solution of the 1mol/L of 60 DEG C, after constantly stirring NaOH solution 1 h in hydrolytic process, film is taken out, obtain polyacrylonitrile hydrolyzed film, with alkali lye residual in rinsed with deionized water film, until rinsing liquid pH value is neutral, obtains PAN and be hydrolyzed film.Through NaOH hydrolysis, form a large amount of carboxyls on PAN film surface.Get previous step to be washed till neutral hydrolysis film and to be immersed in 10 g/L EDC cushioning liquid to activate 6 hours in refrigerator.Configure 5 g/L 3-DIMAPA solution 50 ml, PAN-COO
-film is immersed in solution and at room temperature reacts 24 hours.React rear deionized water the 3-DIMAPA on film surface and cushioning liquid are cleaned up.Then made for upper step film is immersed in the tetrahydrofuran solution containing 2 g 3-bromo-propionic acids, is placed in thermostat water bath 50 DEG C of isothermal reactions 24 hours, obtains Modified Membrane, then clean up with the impurity of deionized water by film surface.Do not damage film through modification through characterizing, wherein 5 g/L 3-DIMAPA Modified Membrane pure water fluxs can maintain 233.89 L/ (m
2h), proteins throughput 72.67 L/ (m
2h), rejection 98.2%, after waterpower cleaning, this film has higher flux recovery rate (90%-95%), and after for several times ultrafiltration cycling, flux is still in higher level, and flux only decays to original 82%, and blank film decays to original 22%.
Embodiment 2
Polyacrylonitrile basement membrane is immersed in the NaOH solution of the 1mol/L of 60 DEG C, after constantly stirring NaOH solution 1 h in hydrolytic process, film is taken out, obtain polyacrylonitrile hydrolyzed film, with alkali lye residual in rinsed with deionized water film, until rinsing liquid pH value is neutral, obtains PAN and be hydrolyzed film.Through NaOH hydrolysis, form a large amount of carboxyls on PAN film surface.Get previous step to be washed till neutral hydrolysis film and to be immersed in 10 g/L EDC cushioning liquid to activate 6 hours in refrigerator.Configure 2 g/L 3-DIMAPA solution 50ml, PAN-COO
-film is immersed in solution and at room temperature reacts 24 hours.React rear deionized water the 3-DIMAPA on film surface and cushioning liquid are cleaned up.Made for upper step film is immersed in the aqueous solution containing 2 g 2-bromoethyl sodium sulfonates, is placed in thermostat water bath 50 DEG C of isothermal reactions 24 hours, obtains Modified Membrane, clean up with the impurity of deionized water by film surface.Do not damage film through modification through characterizing, wherein 2 g/L 3-DIMAPA Modified Membrane pure water fluxs can maintain 198 L/ (m
2h), proteins throughput 64 L/ (m
2h), rejection 99%, after waterpower cleaning, this film has higher flux recovery rate (85%-95%), and after several ultrafiltration cycling, flux only decays to original 81.57%.
Embodiment 3
Polyacrylonitrile basement membrane is immersed in the NaOH solution of the 1mol/L of 60 DEG C, after constantly stirring NaOH solution 1h in hydrolytic process, film is taken out, obtain polyacrylonitrile hydrolyzed film, with alkali lye residual in rinsed with deionized water film, until rinsing liquid pH value is neutral, obtains PAN and be hydrolyzed film.Through NaOH hydrolysis, form a large amount of carboxyls on PAN film surface.Get previous step to be washed till neutral hydrolysis film and to be immersed in 10 g/L EDC cushioning liquid to activate 6 hours in refrigerator.Configure 5 g/L 3-DIMAPA solution 50 ml, PAN-COO
-film is immersed in solution and at room temperature reacts 24 hours.React rear deionized water the 3-DIMAPA on film surface and cushioning liquid are cleaned up.Then film made for upper step is immersed in the oxolane containing 2 g PSs, is placed in thermostat water bath 50 DEG C of isothermal reactions 24 hours, obtains Modified Membrane, clean up with the impurity of deionized water by film surface.Do not damage film through modification through characterizing, pure water flux can maintain 72.28 L/ (m
2h), proteins throughput 37.01 L/ (m
2h), rejection 99%, after waterpower cleaning, this film has higher flux recovery rate (95%-98%), and after several ultrafiltration cycling, flux only decays to original 93%.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any change of expecting without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (4)
1. a polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution, it is characterized in that by comprising the steps to make in interior method: by polyacrylonitrile basement membrane, be immersed in 0.5-1.5 h in the aqueous slkali of 50-70 DEG C, washing, and then activate in the cushioning liquid being immersed in 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, activated hydrolysis film is at room temperature immersed in 20 more than h in 3-dimethylamino propylamine solution, film water is immersed in after washing in 40-60 DEG C of quaternary ammonium reagent and reacts 20 more than h, polyacrylonitrile amphion graft modification milipore filter is obtained through post processing.
2. polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution according to claim 1, described quaternary ammonium reagent is selected from halogenosulfonic acid salt, halogenated acid, sultones.
3. polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution according to claim 1, described quaternary ammonium reagent is selected from the one in 3-bromo-propionic acid, 2-bromoethyl sodium sulfonate, PS.
4. a polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution preparation method, comprises the following steps:
1) polyacrylonitrile ultrafiltration film basement membrane is immersed in the NaOH of 50-70 DEG C of 1-2 mol/L or KOH solution and takes out after 1 h-3 h, with alkali lye residual in rinsed with deionized water film;
2) made for step 1) hydrolysis film is immersed in the cushioning liquid of 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and activates 4 h-8 h, then use washed with de-ionized water 2-4 time;
3) by step 2) made polyacrylonitrile activation hydrolysis film is immersed in the 3-dimethylamino propylamine solution of 1 g/L-10 g/L and reacts 12h-48h, then uses washed with de-ionized water three times;
4) polyacrylonitrile film made for upper step is immersed in 50 DEG C of 3-bromo-propionic acid solution and reacts 12 h-48 h, film is taken out, after rinsed with deionized water 3 times, obtains polyacrylonitrile hydrolyzed modified ultrafiltration membrane.
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| CN109999662A (en) * | 2019-03-26 | 2019-07-12 | 黑龙江八一农垦大学 | A kind of amphoteric ion nanofiltration membrane and preparation method thereof |
| CN110743377B (en) * | 2019-10-21 | 2022-06-21 | 浙江理工大学 | Method for synchronously improving flux and anti-pollution performance of polyamide reverse osmosis composite membrane |
| CN110743383B (en) * | 2019-10-21 | 2023-01-10 | 浙江理工大学 | Modification method for improving permeation flux of polyamide composite membrane |
| CN115704118A (en) * | 2021-08-03 | 2023-02-17 | 安徽东锦服饰有限公司 | Anti-fouling fabric and preparation method thereof |
| CN113522047B (en) * | 2021-08-27 | 2023-03-10 | 山西大学 | D-amino acid chemical grafting modified water treatment ultrafiltration membrane and preparation method thereof |
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