CN113262654A - Water treatment membrane with Fenton catalytic self-cleaning performance and preparation method and application thereof - Google Patents

Water treatment membrane with Fenton catalytic self-cleaning performance and preparation method and application thereof Download PDF

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CN113262654A
CN113262654A CN202110625453.3A CN202110625453A CN113262654A CN 113262654 A CN113262654 A CN 113262654A CN 202110625453 A CN202110625453 A CN 202110625453A CN 113262654 A CN113262654 A CN 113262654A
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block copolymer
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water treatment
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hydroxyl
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张强
王艳
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Nanjing University of Science and Technology
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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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • 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
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

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  • Hydrology & Water Resources (AREA)
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Abstract

The invention discloses a water treatment membrane with Fenton catalytic self-cleaning performance, and a preparation method and application thereof. The method comprises the steps of firstly synthesizing a hydrophilic block polymer containing hydroxyl and a ferrocenyl block copolymer, then mixing polyvinylpyrrolidone, N-methyl pyrrolidone, polysulfone, the hydrophilic block polymer containing hydroxyl and the ferrocenyl block copolymer to prepare a membrane casting solution, standing and defoaming, and then preparing the water treatment membrane with Fenton catalytic self-cleaning performance by a phase conversion method. According to the invention, the block copolymer containing hydroxyl on the side chain and the block copolymer containing ferrocene on the side chain are introduced into the membrane, so that the comprehensive performance can be effectively improved, the hydrophilicity and the anti-fouling effect of the membrane are improved, and the self-cleaning capability is realized.

Description

Water treatment membrane with Fenton catalytic self-cleaning performance and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water treatment membranes, and relates to a water treatment membrane with Fenton catalytic self-cleaning performance, and a preparation method and application thereof.
Background
Membrane technology has become one of the most efficient and economical solutions in selective separation, purification and water treatment over the past few decades. Different membrane technologies such as ultrafiltration, nanofiltration and reverse osmosis are widely used in the fields of wastewater treatment or seawater desalination. However, when treating wastewater, the non-specific interaction between the membrane surface and the contaminants can cause the membrane surface to be severely contaminated. Membrane fouling has always been a bottleneck problem in membrane applications due to the much more complex conditions and separation systems for practical membrane applications. For wastewater treatment, membrane fouling is mainly from macromolecular organic matter, humus, hydrocarbons, bacteria, suspended sludge and inorganic matter. During membrane separation, the transmembrane pressure forces various substances in the separation system to be deposited, adsorbed or accumulated on the membrane surface or internal structure, which inevitably leads to a reduction in membrane separation performance. To maintain a stable flux, higher operating pressures or frequent chemical washes are required, not only increasing operating costs, but also greatly shortening the useful life of the membrane. Therefore, the development of an antifouling film with high antifouling capacity is a key problem for solving the film pollution.
It is well known that membranes can be antifouling modified according to three mechanisms, namely an antifouling mechanism, a fouling release mechanism and a fouling attack mechanism. According to an antifouling mechanism, the antifouling performance can be improved by increasing the hydrophilicity, and a hydration layer formed on the super-hydrophilic surface can prevent hydrophobic pollutants from being adsorbed and deposited on the surface of the membrane. According to the dirt release mechanism, the surface energy of the membrane is reduced, and dirt can be released by minimizing the strength, so that the aim of preventing dirt is fulfilled. According to the fouling attack mechanism, the membrane with catalytic ability can inactivate cells or oxidize and decompose pollutants, and has self-cleaning performance.
In recent years, catalytic membranes have become a new antifouling solution. The catalyst can modify the water treatment membrane by surface coating, surface grafting, mixed doping and other modes to obtain the composite membrane with catalytic self-cleaning performance. Preparing PVDF porous catalytic membrane doped with iron oxide nanoparticles by Alpatova and the like through a phase inversion method, Fe2O3Can be prepared by mixing H2O2Decomposition into hydroxyl radicals, which in turn promotes the oxidation of organic molecules while reducing membrane fouling (a. alpathova, m.meshref, k.n. mcphledans, m.gamal El-Din, Composite polyvinylidene fluoride (PVDF) membrane impregnated with Fe2O3nanoparticles and multiwalled carbon nanotubes for catalytic degradation of organic contaminants, J.Membr.Sci.,490(2015) 227-. Xie et al use Fe-based MOFs as Fenton catalyst to mix with polymer matrix in situ, and make them by phase inversionThe prepared membrane has membrane Fenton catalytic performance (A.T. Xie, J.Y.cui, J.Yang, Y.Y.et. al., Graphene oxide/Fe (III) -based metal-organic frame membrane for enhanced water purification on synthesis and photo-Fenton process, Applied Catalysis B-Environmental,264 (2020)). However, the inorganic particle doped modified films have problems of particle loss, increased film surface roughness, and the like.
Disclosure of Invention
Aiming at the problems of single function, easy pollution, short service life and the like of the existing water treatment membrane, the invention provides a water treatment membrane with the functions of interception and separation and the Fenton catalytic self-cleaning performance, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the preparation method of the water treatment membrane with the Fenton catalytic self-cleaning performance comprises the following steps:
s1, preparation of hydroxyl-terminated polysulfone: dissolving 4,4' -difluoro diphenyl sulfone, bisphenol A and anhydrous potassium carbonate in a mixed solution of N, N-dimethylacetamide and toluene in sequence, reacting for 4-6 hours at 140-160 ℃ in an inert gas atmosphere, then reacting for 6-10 hours at 165-190 ℃, and after the reaction is finished, precipitating, filtering, washing and drying to obtain hydroxyl-terminated polysulfone;
s2, preparation of a macroinitiator: dissolving hydroxyl-terminated polysulfone and triethylamine in dichloromethane, slowly dropwise adding 2-bromo-isobutyryl bromide under the conditions of inert gas atmosphere and ice bath, continuously stirring at room temperature for reaction, and after the reaction is finished, concentrating, precipitating, washing and drying to obtain a macromolecular initiator with a terminal group containing bromine;
s3, preparation of hydrophilic block copolymer containing hydroxyl: dissolving a macroinitiator with a bromine-containing end group, hydroxyethyl acrylate, copper bromide and tris (2-dimethylaminoethyl) amine in dimethyl sulfoxide, adding a copper wire under an inert gas atmosphere, stirring at room temperature to perform a polymerization reaction, and dialyzing and freeze-drying after the reaction is finished to obtain a hydrophilic block copolymer containing hydroxyl;
s4, preparation of ferrocenyl block copolymer: dissolving a hydrophilic block polymer containing hydroxyl, ferrocenecarboxylic acid and 4-dimethylaminopyridine in N, N-dimethylformamide, slowly adding dicyclohexylcarbodiimide under the conditions of inert gas atmosphere and ice bath, continuing stirring at room temperature for reaction, and dialyzing and freeze-drying after the reaction is finished to obtain a ferrocenyl block copolymer;
s5, preparation of a membrane material: uniformly stirring polyvinylpyrrolidone, N-methyl pyrrolidone, polysulfone, a hydrophilic block polymer containing hydroxyl and a ferrocenyl block copolymer to prepare a membrane casting solution, standing and defoaming, and then preparing the water treatment membrane with Fenton catalytic self-cleaning performance by a phase inversion method.
Preferably, in step S1, the molar ratio of difluorodiphenyl sulfone, bisphenol a and potassium carbonate is 1: (1.1-1.2): 3.2.
preferably, in step S1, the volume ratio of N, N-dimethylacetamide to toluene in the mixed solution of N, N-dimethylacetamide and toluene is 1: 1.
Preferably, in step S2, the molar ratio of the hydroxyl-terminated polysulfone to the triethylamine to the 2-bromoisobutyryl bromide is 1: 11.6: 8.7.
preferably, in step S2, the reaction time is 24 hours or more.
Preferably, in step S3, the reaction time is 12 hours or more.
Preferably, in step S4, the reaction time is 24 hours or more.
Preferably, in step S3, the molar ratio of the bromine-terminated macroinitiator, hydroxyethyl acrylate, copper bromide and tris (2-dimethylaminoethyl) amine is 1: (100-200): 1.25: 2.25.
preferably, in step S4, the hydroxyl group-containing hydrophilic block copolymer, ferrocenecarboxylic acid, 4-dimethylaminopyridine and dicyclohexylcarbodiimide are mixed in a molar ratio of 1: (1-2): 1: 1.
preferably, the inert gas is selected from nitrogen, helium, neon or argon.
Preferably, in step S5, the mass ratio of the polyvinylpyrrolidone, the N-methylpyrrolidone, the polysulfone, the hydrophilic block polymer containing a hydroxyl group, and the ferrocenyl block copolymer is 0.4: 7.8: 1.7: 0.1: (0.085-0.255).
Preferably, in step S5, the stirring temperature is 60 to 80 ℃, the stirring time is 12 to 18 hours, and the standing and defoaming time is 6 to 12 hours.
Preferably, in step S5, the phase inversion method comprises the following specific steps: and uniformly scraping and coating the casting solution on a substrate, and carrying out phase splitting in a gel bath to obtain the water treatment membrane.
Preferably, in step S5, the thickness of the coating of the casting solution on the substrate is 150-200 μm.
Preferably, in step S5, the gel bath is water or a mixed solution of water and ethanol, and the temperature of the gel bath is 20 to 30 ℃.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the organic polymer with catalytic capability is adopted for doping modification, so that the problems of loss and high roughness of the existing inorganic doping modified catalytic membrane are solved;
(2) according to the water treatment membrane with Fenton catalytic capability, the block copolymer containing hydroxyl on the side chain and the block copolymer containing ferrocene on the side chain are introduced, so that the comprehensive performance can be effectively improved, the hydrophilicity and the anti-fouling effect of the membrane are improved, and the self-cleaning capability is realized;
(3) the water treatment membrane has the functions of interception and separation, has the capabilities of catalysis and self cleaning, is simple in preparation method and easy to control process conditions, and is beneficial to efficient production of the membrane.
Drawings
FIG. 1 is a graph showing comparison of Fenton catalytic effects of water treatment membranes prepared in comparative example and example;
fig. 2 is a graph comparing the effect of retention and flux of the water treatment membrane prepared in the comparative example and example.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
S1, preparation of hydroxyl-terminated polysulfone: according to the molar ratio of difluoro diphenyl sulfone, bisphenol A and potassium carbonate being 1: 1.2: 3.2, dissolving 4,4' -difluoro diphenyl sulfone, bisphenol A and anhydrous potassium carbonate in a mixed solution of 100ml of N, N-dimethylacetamide and 100ml of toluene in sequence, reacting for 4 hours at 155 ℃ in a nitrogen atmosphere, reacting for 6 hours at 190 ℃, and then precipitating, filtering, washing and drying to obtain the hydroxyl-terminated polysulfone.
S2, preparation of a macroinitiator: according to the molar ratio of 1: 11.6: 8.7, dissolving the hydroxyl-terminated polysulfone and triethylamine into dichloromethane, slowly dropwise adding 2-bromoisobutyryl bromide under the conditions of nitrogen atmosphere and ice bath, continuously stirring at room temperature for reaction for 24 hours, and then concentrating, precipitating, washing and drying to obtain the macromolecular initiator with bromine at the end group.
S3, preparation of hydrophilic block copolymer containing hydroxyl: according to the mol ratio of the macromolecular initiator with bromine at the end group, hydroxyethyl acrylate, copper bromide and tris (2-dimethylaminoethyl) amine, the ratio is 1: 100: 1.25: 2.25. dissolving a macroinitiator with bromine at the end group, hydroxyethyl acrylate, copper bromide and tris (2-dimethylaminoethyl) amine in a dimethyl sulfoxide solvent, adding a magneton wound with a 3cm copper wire under the nitrogen atmosphere, carrying out polymerization reaction for 12 hours at room temperature under the stirring condition, dialyzing, and freeze-drying to obtain the hydrophilic block polymer containing hydroxyl.
S4, preparation of ferrocenyl block copolymer: according to the molar ratio of hydrophilic block polymer containing hydroxyl, ferrocenecarboxylic acid, 4-dimethylaminopyridine and dicyclohexylcarbodiimide of 1: 2: 1: dissolving hydroxyl-containing hydrophilic block polymer, ferrocenecarboxylic acid and 4-dimethylaminopyridine in N, N-dimethylformamide, slowly adding dicyclohexylcarbodiimide under the conditions of nitrogen atmosphere and ice bath, continuously stirring at room temperature for reaction for 24 hours, dialyzing, and freeze-drying to obtain the ferrocenyl block copolymer.
S5, preparation of a membrane material: according to the mass ratio of polyvinylpyrrolidone, N-methyl pyrrolidone, polysulfone, hydrophilic block copolymer containing hydroxyl and ferrocenyl block copolymer of 0.4: 7.8: 1.7: 0.1: 0.085, mixing polyvinylpyrrolidone, N-methyl pyrrolidone, polysulfone, hydrophilic block copolymer containing hydroxyl and ferrocenyl block copolymer, stirring at 60 ℃ for 12 hours to prepare casting solution, standing for 12 hours, removing bubbles, uniformly scraping and coating the casting solution on a substrate to form a thickness of 180 mu m in the phase inversion process, carrying out phase separation in a water bath at 25 ℃, and preparing the water treatment membrane with Fenton catalytic self-cleaning performance by the phase inversion process.
Example 2
This example is essentially the same as example 1, except that the mass ratio of polyvinylpyrrolidone, N-methylpyrrolidone, polysulfone, hydrophilic block copolymer having a hydroxyl group, and ferrocenyl block copolymer described in step S5 was 0.4: 7.8: 1.7: 0.1: 0.255.
comparative example 1
According to the comparative example, the casting solution does not contain the hydroxyl-containing hydrophilic block copolymer and ferrocenyl block copolymer in example 1, the proportion of other components of the casting solution is unchanged, and other steps are the same as those in example 1.
Comparative example 2
This example provides a hydrophilically modified polysulfone membrane, in this comparative example, the casting solution did not contain the ferrocenyl block copolymer of example 1, the ratio of other components of the casting solution was unchanged, and the other steps were the same as in example 1.
Comparative example 3
This comparative example is substantially the same as example 1, and the mass ratio of polyvinylpyrrolidone, N-methylpyrrolidone, polysulfone, and hydrophilic block copolymer containing hydroxyl group in step S5 is not changed, except that the proportion of ferrocenyl block copolymer is increased, specifically, the proportion of polyvinylpyrrolidone, N-methylpyrrolidone, polysulfone, hydrophilic block copolymer containing hydroxyl group, ferrocenyl block copolymer is: 0.4: 7.8: 1.7: 0.1: 0.285, the increased proportion of ferrocenyl block copolymer causes the poor compatibility of the casting solution and the poor film forming effect.
The film samples obtained in examples 1-2 and comparative examples 1-2 above were subjected to a roughness test by the following method:
the surface roughness of all films was characterized using an atomic force microscope (AFM, MFP-3D Origin +, Oxford Instruments, UK).
The fenton test was performed on all the samples obtained in the above examples and comparative examples, and the test method was as follows:
putting a water treatment membrane or a hydrophobic polysulfone membrane or a hydrophilic modified polysulfone membrane with Fenton catalytic self-cleaning capacity into methylene blue simulated dye wastewater (50mg/L of methylene blue solution), wherein the adopted conditions of the methylene blue solution comprise: the temperature is 55 ℃, the pH value is 3, and the concentration of hydrogen peroxide is 0.15M. Periodically taking a methylene blue solution, measuring the absorbance change of the methylene blue solution under the absorption wavelength of 664nm by using an ultraviolet spectrophotometer, and calculating the catalytic degradation efficiency according to the following formula:
Removal Rate＝(1-At/A0)×100％，
wherein A is0Denotes the initial methylene blue solution absorbance, AtThe absorbance at the interval time t is shown.
The samples obtained in examples 1-2 and comparative examples 1-2 above were subjected to the retention test as follows:
in Congo red simulated dye wastewater (50mg/L Congo red solution), the test pressure is 4bar, and the interception effect is evaluated by a membrane evaluator. Periodically taking the Congo red solution, measuring the absorbance change of the Congo red solution under the absorption wavelength of 497nm by using an ultraviolet spectrophotometer, and calculating the catalytic degradation efficiency according to the following formula:
Removal Rate＝(1-At/A0)×100％，
the roughness, catalytic effect and retention data are as follows:
the roughness test result shows that the roughness is basically unchanged before and after doping the hydroxyl-containing hydrophilic block copolymer or ferrocenyl block copolymer, and still remains at a very low level. Specific roughness values are shown in table 1.
TABLE 1 film surface roughness comparison
Film Example 1 Example 2 Comparative example 1 Comparative example 2
Ra 17.6 18.9 17.7 18.2
The fenton test result is shown in fig. 1, and it can be seen from the figure that the membranes prepared in examples 1 and 2 show excellent fenton performance compared with the comparative example, and the catalytic effect of examples 1 and 2 on methylene blue can reach 99% within 60min, because the ferrocene block copolymer plays a catalytic role and endows the membrane with a catalytic function.
The results of the rejection tests are shown in fig. 2, and it can be seen from the figure that the prepared membranes all show excellent rejection (all > 97%), but the flux of the congo red solutions of comparative example 2, example 1 and example 2 is improved significantly, approaching 4 times that of comparative example 1, which is mainly due to the hydrophilic polymer containing hydroxyl groups, which imparts hydrophilicity to the membranes and contributes to the improvement of flux.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art can make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The preparation method of the water treatment membrane with the Fenton catalytic self-cleaning performance is characterized by comprising the following steps of:
s1, preparation of hydroxyl-terminated polysulfone: dissolving 4,4' -difluoro diphenyl sulfone, bisphenol A and anhydrous potassium carbonate in a mixed solution of N, N-dimethylacetamide and toluene in sequence, reacting for 4-6 hours at 140-160 ℃ in an inert gas atmosphere, then reacting for 6-10 hours at 165-190 ℃, and after the reaction is finished, precipitating, filtering, washing and drying to obtain hydroxyl-terminated polysulfone;
s2, preparation of a macroinitiator: dissolving hydroxyl-terminated polysulfone and triethylamine in dichloromethane, slowly dropwise adding 2-bromo-isobutyryl bromide under the conditions of inert gas atmosphere and ice bath, continuously stirring at room temperature for reaction, and after the reaction is finished, concentrating, precipitating, washing and drying to obtain a macromolecular initiator with a terminal group containing bromine;
s3, preparation of hydrophilic block copolymer containing hydroxyl: dissolving a macroinitiator with a bromine-containing end group, hydroxyethyl acrylate, copper bromide and tris (2-dimethylaminoethyl) amine in dimethyl sulfoxide, adding a copper wire under an inert gas atmosphere, stirring at room temperature to perform a polymerization reaction, and dialyzing and freeze-drying after the reaction is finished to obtain a hydrophilic block copolymer containing hydroxyl;
s4, preparation of ferrocenyl block copolymer: dissolving a hydrophilic block polymer containing hydroxyl, ferrocenecarboxylic acid and 4-dimethylaminopyridine in N, N-dimethylformamide, slowly adding dicyclohexylcarbodiimide under the conditions of inert gas atmosphere and ice bath, continuing stirring at room temperature for reaction, and dialyzing and freeze-drying after the reaction is finished to obtain a ferrocenyl block copolymer;
s5, preparation of a membrane material: uniformly stirring polyvinylpyrrolidone, N-methyl pyrrolidone, polysulfone, a hydrophilic block polymer containing hydroxyl and a ferrocenyl block copolymer to prepare a membrane casting solution, standing and defoaming, and then preparing the water treatment membrane with Fenton catalytic self-cleaning performance by a phase inversion method.
2. The method according to claim 1, wherein in step S1, the molar ratio of difluorodiphenyl sulfone, bisphenol a, and potassium carbonate is 1: (1.1-1.2): 3.2; in the mixed solution of N, N-dimethylacetamide and toluene, the volume ratio of N, N-dimethylacetamide to toluene is 1: 1.
3. The method according to claim 1, wherein in step S2, the molar ratio of the hydroxyl-terminated polysulfone to the triethylamine to the 2-bromoisobutyryl bromide is 1: 11.6: 8.7.
4. the method according to claim 1, wherein in step S2 or S3 or S4, the reaction time is 24 hours or more; the inert gas is selected from nitrogen, helium, neon or argon.
5. The method according to claim 1, wherein in step S3, the molar ratio of the bromine-terminated macroinitiator, hydroxyethyl acrylate, copper bromide and tris (2-dimethylaminoethyl) amine is 1: (100-200): 1.25: 2.25.
6. the method according to claim 1, wherein in step S4, the hydroxyl group-containing hydrophilic block copolymer, ferrocenecarboxylic acid, 4-dimethylaminopyridine and dicyclohexylcarbodiimide are mixed in a molar ratio of 1: (1-2): 1: 1; in step S5, the mass ratio of polyvinylpyrrolidone, N-methylpyrrolidone, polysulfone, hydrophilic block polymer containing hydroxyl group, and ferrocenyl block copolymer is 0.4: 7.8: 1.7: 0.1: (0.085-0.255).
7. The method according to claim 1, wherein in step S5, the stirring temperature is 60 to 80 ℃, the stirring time is 12 to 18 hours, and the standing defoaming time is 6 to 12 hours; the phase inversion method comprises the following specific steps: and uniformly scraping and coating the casting solution on a substrate, and carrying out phase splitting in a gel bath to obtain the water treatment membrane.
8. The method according to claim 7, wherein in step S5, the thickness of the coating of the casting solution on the substrate is 150-200 μm, the gel bath is water or a mixed solution of water and ethanol, and the temperature of the gel bath is 20-30 ℃.
9. A water treatment membrane produced by the production method according to any one of claims 1 to 8.
10. Use of a water treatment membrane according to claim 9 in water treatment.
CN202110625453.3A 2021-06-04 2021-06-04 Water treatment membrane with Fenton catalytic self-cleaning performance and preparation method and application thereof Withdrawn CN113262654A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105032220A (en) * 2015-09-08 2015-11-11 南京工业大学 Preparation method of permanent hydrophilic type polysulfone ultrafiltration membrane
CN110975626A (en) * 2019-12-09 2020-04-10 西安建筑科技大学 Preparation method of photo-Fenton catalytic self-cleaning super-hydrophilic PVDF ultrafiltration membrane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105032220A (en) * 2015-09-08 2015-11-11 南京工业大学 Preparation method of permanent hydrophilic type polysulfone ultrafiltration membrane
CN110975626A (en) * 2019-12-09 2020-04-10 西安建筑科技大学 Preparation method of photo-Fenton catalytic self-cleaning super-hydrophilic PVDF ultrafiltration membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YAN WANG等: "Self-cleaning catalytic membrane for water treatment via an integration of Heterogeneous Fenton and membrane process", 《JOURNAL OF MEMBRANE SCIENCE》 *

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Application publication date: 20210817