CN106621833A - Preparation method of ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles - Google Patents

Preparation method of ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles Download PDF

Info

Publication number
CN106621833A
CN106621833A CN201611179911.0A CN201611179911A CN106621833A CN 106621833 A CN106621833 A CN 106621833A CN 201611179911 A CN201611179911 A CN 201611179911A CN 106621833 A CN106621833 A CN 106621833A
Authority
CN
China
Prior art keywords
graphene oxide
tio
composite particles
solution
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611179911.0A
Other languages
Chinese (zh)
Inventor
许航
丁明梅
陈卫
李洋
王康
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hohai University HHU
Original Assignee
Hohai University HHU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hohai University HHU filed Critical Hohai University HHU
Priority to CN201611179911.0A priority Critical patent/CN106621833A/en
Publication of CN106621833A publication Critical patent/CN106621833A/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/66Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68Polysulfones; Polyethersulfones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a preparation method of an ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles. The preparation method comprises the following steps: (1) preparing the nitrogen-doped graphene oxide / TiO2 composite particles; (2) adding an organic solvent in the nitrogen-doped graphene oxide / TiO2 composite particles, uniformly dispersing, then adding a membrane material and a membrane additive, and mixing evenly to obtain a casting membrane solution; and (3) after defoaming of the casting membrane solution stops, pouring the casting membrane solution on the surface of a clean and smooth flat plate, stably and rapidly scraping the casting membrane solution by using a membrane blade, and placing the casting membrane solution in a gel phase to obtain the ultrafiltration membrane. The polysulfone ultrafiltration membrane with high hydrophilicity and anti-fouling performance is prepared by phase inversion, a water contact angle of the prepared polysulfone ultrafiltration membrane is reduced obviously, and is reduced to be about 61 degrees from about 88 degrees, and therefore, the anti-fouling ability of the membrane is improved.

Description

One kind utilizes nitrating graphene oxide/TiO2Composite particles strengthen the ultrafiltration of resistance tocrocking The preparation method of film
Technical field
The present invention relates to a kind of preparation method of milipore filter, more particularly, to a kind of nitrating graphene oxide/TiO is utilized2 Composite particles strengthen the preparation method of the milipore filter of resistance tocrocking.
Background technology
Ultrafiltration is a kind of membrane separating process, is colloid, bulky grain and molecular weight phase in trap water under ambient pressure effect To higher material, and water and little particles of solute pass through the separation process of film.Because hyperfiltration technique has normal-temperature operation, process Without it is covert, energy consumption is low, separative efficiency is high the advantages of, drink water purifying, petrochemical industry, bio-pharmaceuticals, video, metallurgy etc. again at present Industry is widely applied.
PS membrane has strong oxidative resistance, and with cheap and easy to get, good mechanical strength, the close property of resistance to compression and chemically stable Property, heat resistance and the advantages of wide pH value use ranges, but its hydrophobicity is also that people all knows, the main performance of its harm Easily absorption is produced in hydrophobic solutes on film surface and deposited, cause fouling membrane, reduce the performance and the service life for shortening film of film. Therefore, PS membrane is carried out hydrophilically modified, improves its contamination resistance very necessary.
At present, hydrophilically modified method is carried out to milipore filter mainly modified surface, blending and modifying and chemical modification etc.. Relative to other two kinds of method of modifying, blending and modifying has operation relatively easy, and modified effect is good, the advantages of economical and practical.Have Machine-inorganic blending operations are simple, excellent performance, add hydrophilic inorganic nano particle to increase film surface hydrophilicity, reduce film Pollution, while improve film mechanical performance, be study hotspot in recent years.
TiO2Particle contains nano-TiO due to ultrahydrophilic, extremely strong photocatalytic and the function such as nontoxic, preparation2Have Machine-inorganic hybridization membrane material has caused the extensive concern of researcher with the mutual supplement with each other's advantages for realizing both.But TiO2With easily reunion The shortcoming of property, have impact on its extensive application in field of membrane material.Nitrating graphene oxide, as the derivative of Graphene, tool There are the properties such as good electric conductivity, hydrophily, heat endurance and mechanical strength, it is used as TiO2Carrier can greatly improve The dispersiveness of titanium dioxide and hydrophily.
The content of the invention
The technical problem to be solved is the defect for overcoming prior art, there is provided one kind utilizes nitrating graphite oxide Alkene/TiO2Composite particles strengthen the preparation method of the milipore filter of resistance tocrocking.The present invention is prepared using phase inversion has high parent The polysulphone super-filter membrane of aqueous and resistance tocrocking, the water contact angle of made polysulphone super-filter membrane is substantially reduced, is reduced to from 88 ° or so 61 ° or so, improve the contamination resistance of film.
To solve above-mentioned technical problem, the present invention provides a kind of using nitrating graphene oxide/TiO2Composite particles strengthen The preparation method of the milipore filter of resistance tocrocking, is characterized in that, comprise the following steps:
(1)Nitrogen oxidation Graphene/TiO2The preparation of composite particles
Weigh graphene oxide to be placed in beaker, with distillation water dissolves, ultrasonic vibration 1h makes graphene oxide be uniformly dispersed;Claim Take urea to be dissolved into graphene oxide solution, stir;The solution for preparing is put into reactor and is heated, obtain black Solution;Dark solution is added and obtain nitrating graphene oxide particle after distilled water cyclic washing and freeze-drying;By nitrating oxygen Graphite alkene and TiO2Particle is placed in beaker and dissolves, and after ultrasonic vibration 30min, is put into reactor and heats, and obtains grey molten Liquid;Grey solution is added and obtain nitrating graphene oxide/TiO after distilled water cyclic washing and freeze-drying2Composite particles;
(2)Nitrating graphene oxide/TiO2After adding organic solvent, decentralized processing uniform in composite particles, addition membrane material, Film additive, obtains casting solution after being well mixed;
(3)After by casting solution discontinuous degassing, clean smooth planar surface is poured over, after steadily being scraped rapidly with knifing machine, is put In entering gel phase, milipore filter is obtained.The gel is mutually using water, water and solvent mixed liquor, water and absolute ethyl alcohol mixed liquor, air In one kind, wherein, solvent mixed liquor be 1-METHYLPYRROLIDONE, N-N- dimethylformamides, N-N- dimethyl acetamides in A kind of constituted mixed liquor;To gel mutually this process elapsed time referred to as dry journey is put into after knifing, do The length of journey can have a strong impact on the pore-size distribution on prepared film surface, therefore it is preferred that the dry journey is 0~2min.
Further, above-mentioned steps(1)In, the graphene oxide is 1 with the mass ratio of urea:4.
Further, above-mentioned steps(1)In, answer heating condition in kettle to be to heat 24 hours at 180 DEG C described.
Further, above-mentioned steps(1)In, the nitrating graphene oxide and TiO2The mass ratio of particle is 7:3.
Further, the TiO2Particle is prepared by sol-gal process, and concrete operation method is as follows:
Solution A:By butyl titanate and absolute ethyl alcohol by volume 1:4 are well mixed in beaker;
B solution:By absolute ethyl alcohol, pure water, glacial acetic acid by volume 5:2:1 prepares mixed solution, and adjusts PH=2 with watery hydrochloric acid, B solution is dropwise added drop-wise in solution A, and persistently stirs 30min, it is stirred after, by the static 3h gels of mixed solution;
Above-mentioned spawn is placed in air dry oven 24h is dried at 100 DEG C, powdery is ground to form after cooling, then be placed in 500 DEG C of calcining 2h are heated to the speed of 2 DEG C/min in resistance furnace, are taken out after natural cooling and is obtained TiO2Particle.
Further, above-mentioned steps(2)In, the nitrating graphene oxide/TiO2The addition content of composite particles is 0.1~0.8%, content refers to the mass fraction relative to casting solution.Nitrating graphene oxide/TiO2The addition of composite particles The performance tool of milipore filter is had a significant impact, because nitrating graphene oxide/TiO2Composite particles add membership to affect split-phase mistake Journey, so as to affect the aperture of film, with nitrating graphene oxide/TiO2The increase of composite particles addition, the aperture of milipore filter First increases and then decreases.
Further, above-mentioned steps(2)In, the organic solvent be 1-METHYLPYRROLIDONE, N-N- dimethylformamides, One kind in N-N- dimethyl acetamides, organic solvent content is 75~90%, and content refers to the quality point relative to casting solution Number.
Further, above-mentioned steps(2)In, described film additive is polyvinyl pyrrolidone, polyethylene glycol, poly- second One kind in enol, the content of film additive is 0~4%, and content refers to the mass fraction relative to casting solution.
Further, above-mentioned steps(2)In, described decentralized processing is processed using ultrasonication, stir process, concussion In one kind.Nitrating graphene oxide/TiO can be made2Composite particles are uniformly dispersed in organic solvent again, and preferably described divides The scattered time is 2h.
Further, above-mentioned steps(2)In, described membrane material is polysulfones, and the content of membrane material is 16~25%, content Refer to the mass fraction relative to casting solution.
The beneficial effect that the present invention is reached:
(1)Nitrating graphene oxide/TiO2Composite particles can uniformly, be well dispersed into solvent or casting solution, this is very big Improve nitrating graphene oxide/TiO2Contact and compatibility of the composite particles with film, is more beneficial for playing its own feature;
(2)Nitrating graphene oxide/TiO2The addition of composite particles makes the water contact angle of milipore filter substantially reduce, from 88 ° or so 61 ° or so are reduced to, the antifouling property of film is improve;
(3)Nitrating graphene oxide/the TiO of the present invention2Composite particles preparation method is simple, it is easy to industrialized production application.
Description of the drawings
Fig. 1 is embodiment 1~4 with ultrafiltration membrane surface water contact angle in comparative example with nitrating graphene oxide/TiO2It is compound The change of granule content;
Fig. 2 is embodiment 1~4 with ultrafiltration membrane surface protein adsorption quantity in comparative example with nitrating graphene oxide/TiO2Compound The change of grain content.
Specific embodiment
Below in conjunction with the accompanying drawings the invention will be further described.Following examples are only used for clearly illustrating the present invention Technical scheme, and can not be limited the scope of the invention with this.
Embodiment 1
Present embodiments provide a kind of containing 0.1% nitrating graphene oxide/TiO2The preparation method of composite particles polysulphone super-filter membrane, Comprise the following steps that:
(1)350mg graphene oxides are placed in beaker, add 90mL deionized waters, ultrasonic vibration 1h uniformly to be aoxidized Graphene solution.1.2g urea is added toward graphene oxide solution, and persistently stirs 1h and obtain uniform mixed solution.Will be mixed Conjunction solution is put into 150mL reactors and heats 24h at 180 DEG C.Question response kettle is naturally cooled to after room temperature, by the black for obtaining Solid deionized water is rinsed 3 times repeatedly, and nitrating graphene oxide is obtained after freeze-drying;
(2)Solution A:To be well mixed in 10mL butyl titanates and 40mL absolute ethyl alcohol beakers.B solution:By absolute ethyl alcohol, pure Water, glacial acetic acid take respectively 10mL, 4mL, 2mL and are well mixed, and adjust PH=2 with watery hydrochloric acid.B solution is dropwise added drop-wise to solution A In, and persistently stir 30min.After stirred, by the static 3h gels of mixed solution.Above-mentioned spawn is placed in into air blast 24h is dried at 100 DEG C in drying box, powdery is ground to form after cooling, then be placed in resistance furnace and be heated to the speed of 2 DEG C/min 500 DEG C of calcining 2h, take out after natural cooling and obtain TiO2Particle;
(3)Take 350mg nitratings graphene oxide and 210mg TiO2In being placed in beaker, 100mL water is added to obtain under ultrasound condition To uniform mixed liquor.Mixed solution is put into 150mL reactors and heats 24h at 180 DEG C.Question response kettle naturally cools to room Wen Hou, the gray solid deionized water for obtaining is rinsed 3 times repeatedly, and nitrating graphene oxide/TiO is obtained after freeze-drying2 Composite particles;
(4)By 100mg nitratings graphene oxide/TiO2Composite particles are scattered in 78.9gN- crassitudes under ultrasound condition Ketone(NMP)In, after ultrasonic 2h, PVP 3g, polysulfones 18g are added to the solution under stirring, stir at 50 DEG C 6h is mixed, uniform casting solution is formed;
(5)By the static 24h deaerations of casting solution.After deaeration, at ambient temperature, using knifing by casting solution on a glass Machine(Its scraper is 100 μm)Film is uniformly scraped on a glass, and is immediately moved into coagulation bath(Water)After 1~2min visible film from It is dynamic to depart from glass plate;24h is soaked in deionized water, it is ensured that phase transfer completely;Film is placed between two layers of filter paper, greenhouse wind Dry, preparation is completed.
Containing 0.1% nitrating graphene oxide/TiO2Experiment is investigated in the protein absorption of composite particles modified polysulfone film, specifically Operation is as follows:
The milipore filter that one prepares is cut into the diaphragm of diameter 2.5cm, the bovine serum albumen solution containing 500mg/L is entered In, under the rotating speed of 100r/min, adsorb 24h, by determined by ultraviolet spectrophotometry solution remain protein content, so as to The amount of absorption is drawn, experimental result is shown in Fig. 2.
Figure it is seen that containing 0.1% nitrating graphene oxide/TiO2The protein 24h of the PS membrane of composite particles inhales Attached amount is relatively low, with good protein contamination.
Embodiment 2~4
Only change nitrating graphene oxide/TiO2The content of composite particles is 0.3%, 0.5% and 0.8%, other same embodiments of operation 1, gained nitrating graphene oxide/TiO2The modified PS membrane of composite particles has different antipollution effects, sees Fig. 2.
Embodiment 5~6
Organic solvent in embodiment 1 is changed the one kind made in N-N- dimethylformamides, N-N- dimethyl acetamides, other behaviour Make with embodiment 1, gained nitrating graphene oxide/TiO2The antipollution effect and embodiment 1 of the modified PS membrane of composite particles It is essentially identical.
Embodiment 7~8
One kind that film additive in embodiment 1 is changed in making polyethylene glycol, polyvinyl alcohol, other operations are with embodiment 1, gained Nitrating graphene oxide/TiO2The antipollution effect of the modified PS membrane of composite particles is substantially the same manner as Example 1.
Comparative example 1
It is added without nitrating graphene oxide/TiO2To in PS membrane, other operations are with embodiment 1, gained PS membrane for composite particles Resistance tocrocking is poor, sees Fig. 2.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, on the premise of without departing from the technology of the present invention principle, some improvement and deformation can also be made, these improve and deform Also should be regarded as protection scope of the present invention.

Claims (10)

1. it is a kind of to utilize nitrating graphene oxide/TiO2Composite particles strengthen the preparation method of the milipore filter of resistance tocrocking, and it is special Levying is, comprises the following steps:
(1)Nitrogen oxidation Graphene/TiO2The preparation of composite particles
Weigh graphene oxide to be placed in beaker, with distillation water dissolves, ultrasonic vibration 1h makes graphene oxide be uniformly dispersed;Claim Take urea to be dissolved into graphene oxide solution, stir;The solution for preparing is put into reactor and is heated, obtain black Solution;Dark solution is added and obtain nitrating graphene oxide particle after distilled water cyclic washing and freeze-drying;By nitrating oxygen Graphite alkene and TiO2Particle is placed in beaker and dissolves, and after ultrasonic vibration 30min, is put into reactor and heats, and obtains grey molten Liquid;Grey solution is added and obtain nitrating graphene oxide/TiO after distilled water cyclic washing and freeze-drying2Composite particles;
(2)Nitrating graphene oxide/TiO2After adding organic solvent, decentralized processing uniform in composite particles, membrane material, film are added Additive, obtains casting solution after being well mixed;
(3)After by casting solution discontinuous degassing, clean smooth planar surface is poured over, after steadily being scraped rapidly with knifing machine, is put In entering gel phase, milipore filter is obtained.
2. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(1)In, the graphene oxide is 1 with the mass ratio of urea:4.
3. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(1)In, answer heating condition in kettle to be that heating 24 is little at 180 DEG C described When.
4. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(1)In, the nitrating graphene oxide and TiO2The mass ratio of particle is 7:3.
5. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, the TiO2Particle is prepared by sol-gal process, and concrete operation method is as follows:
Solution A:By butyl titanate and absolute ethyl alcohol by volume 1:4 are well mixed in beaker;
B solution:By absolute ethyl alcohol, pure water, glacial acetic acid by volume 5:2:1 prepares mixed solution, and adjusts PH=2 with watery hydrochloric acid, B solution is dropwise added drop-wise in solution A, and persistently stirs 30min, it is stirred after, by the static 3h gels of mixed solution;
Above-mentioned spawn is placed in air dry oven 24h is dried at 100 DEG C, powdery is ground to form after cooling, then be placed in 500 DEG C of calcining 2h are heated to the speed of 2 DEG C/min in resistance furnace, are taken out after natural cooling and is obtained TiO2Particle.
6. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(2)In, the nitrating graphene oxide/TiO2The addition of composite particles Content is 0.1~0.8%, and content refers to the mass fraction relative to casting solution.
7. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(2)In, the organic solvent is 1-METHYLPYRROLIDONE, N-N- dimethyl One kind in formamide, N-N- dimethyl acetamides, organic solvent content is 75~90%, and content is referred to relative to casting solution Mass fraction.
8. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(2)In, described film additive is polyvinyl pyrrolidone, poly- second two One kind in alcohol, polyvinyl alcohol, the content of film additive is 0~4%, and content refers to the mass fraction relative to casting solution.
9. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(2)In, described decentralized processing using ultrasonication, stir process, One kind in concussion process, described jitter time is 2h.
10. according to claim 1 a kind of using nitrating graphene oxide/TiO2Composite particles strengthen the super of resistance tocrocking The preparation method of filter membrane, is characterized in that, above-mentioned steps(2)In, described membrane material is polysulfones, the content of membrane material is 16~ 25%, content refers to the mass fraction relative to casting solution.
CN201611179911.0A 2016-12-19 2016-12-19 Preparation method of ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles Pending CN106621833A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611179911.0A CN106621833A (en) 2016-12-19 2016-12-19 Preparation method of ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611179911.0A CN106621833A (en) 2016-12-19 2016-12-19 Preparation method of ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles

Publications (1)

Publication Number Publication Date
CN106621833A true CN106621833A (en) 2017-05-10

Family

ID=58833832

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611179911.0A Pending CN106621833A (en) 2016-12-19 2016-12-19 Preparation method of ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles

Country Status (1)

Country Link
CN (1) CN106621833A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107552082A (en) * 2017-09-29 2018-01-09 河海大学 A kind of quaternary multifunction magnetic nano composite material and preparation method thereof
CN108176232A (en) * 2017-12-30 2018-06-19 孙祎 A kind of preparation method of the charged membrane material of pollution-resistant
CN108479424A (en) * 2018-04-02 2018-09-04 合肥国轩高科动力能源有限公司 Preparation method of modified polyvinylidene fluoride membrane
CN108927225A (en) * 2018-06-27 2018-12-04 浙江工业大学膜分离与水处理协同创新中心湖州研究院 A kind of photocatalysis membrana preparation method for dyestuff degradation
CN109453679A (en) * 2018-10-30 2019-03-12 江苏理工学院 A kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane
CN111715079A (en) * 2020-05-20 2020-09-29 嘉兴市轩禾园艺技术有限公司 Multifunctional film material and preparation method and application thereof
CN111760461A (en) * 2020-06-24 2020-10-13 上海应用技术大学 Preparation method of polyvinylidene fluoride mixed matrix film
CN112774464A (en) * 2020-12-17 2021-05-11 中国科学院过程工程研究所 Forward osmosis composite membrane and preparation method and application thereof
CN113068903A (en) * 2021-03-26 2021-07-06 莆田市协诚鞋业有限公司 Antifouling and antibacterial upper material and preparation method thereof
CN113877427A (en) * 2021-10-14 2022-01-04 福建工程学院 Preparation method of antibacterial and anti-fouling regenerated cellulose composite ultrafiltration membrane, composite ultrafiltration membrane and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102921444A (en) * 2012-10-26 2013-02-13 东华大学 Method for preparing P25/nitrogen-doped graphene composite material
CN105000548A (en) * 2014-04-22 2015-10-28 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of novel three-dimensional nitrogen doped graphene composite material system
CN105126646A (en) * 2015-08-28 2015-12-09 西南石油大学 Titanium dioxide/halloysite nanotube compound polyvinylidene fluoride ultrafiltration membrane and preparation method thereof
CN105233706A (en) * 2015-09-23 2016-01-13 三达膜科技(厦门)有限公司 Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof
CN106159228A (en) * 2016-07-26 2016-11-23 广东工业大学 A kind of nitrogen-doped graphene metal oxide nano composite material and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102921444A (en) * 2012-10-26 2013-02-13 东华大学 Method for preparing P25/nitrogen-doped graphene composite material
CN105000548A (en) * 2014-04-22 2015-10-28 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of novel three-dimensional nitrogen doped graphene composite material system
CN105126646A (en) * 2015-08-28 2015-12-09 西南石油大学 Titanium dioxide/halloysite nanotube compound polyvinylidene fluoride ultrafiltration membrane and preparation method thereof
CN105233706A (en) * 2015-09-23 2016-01-13 三达膜科技(厦门)有限公司 Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof
CN106159228A (en) * 2016-07-26 2016-11-23 广东工业大学 A kind of nitrogen-doped graphene metal oxide nano composite material and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MAHENDRA KUMAR等: "Preparation and characterization of low fouling novel hybrid ultrafiltration membranes based on the blends of GO−TiO2nanocomposite and polysulfone for humic acid removal", 《SCIENCEDIRECT》 *
罗春华等主编: "《材料化学专业综合实验》", 31 July 2015, 机械工业出版社 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107552082A (en) * 2017-09-29 2018-01-09 河海大学 A kind of quaternary multifunction magnetic nano composite material and preparation method thereof
CN108176232A (en) * 2017-12-30 2018-06-19 孙祎 A kind of preparation method of the charged membrane material of pollution-resistant
CN108479424A (en) * 2018-04-02 2018-09-04 合肥国轩高科动力能源有限公司 Preparation method of modified polyvinylidene fluoride membrane
CN108927225A (en) * 2018-06-27 2018-12-04 浙江工业大学膜分离与水处理协同创新中心湖州研究院 A kind of photocatalysis membrana preparation method for dyestuff degradation
CN109453679A (en) * 2018-10-30 2019-03-12 江苏理工学院 A kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane
CN111715079A (en) * 2020-05-20 2020-09-29 嘉兴市轩禾园艺技术有限公司 Multifunctional film material and preparation method and application thereof
CN111760461A (en) * 2020-06-24 2020-10-13 上海应用技术大学 Preparation method of polyvinylidene fluoride mixed matrix film
CN111760461B (en) * 2020-06-24 2022-08-23 上海应用技术大学 Preparation method of polyvinylidene fluoride mixed matrix membrane
CN112774464A (en) * 2020-12-17 2021-05-11 中国科学院过程工程研究所 Forward osmosis composite membrane and preparation method and application thereof
CN112774464B (en) * 2020-12-17 2022-04-08 中国科学院过程工程研究所 Forward osmosis composite membrane and preparation method and application thereof
CN113068903A (en) * 2021-03-26 2021-07-06 莆田市协诚鞋业有限公司 Antifouling and antibacterial upper material and preparation method thereof
CN113877427A (en) * 2021-10-14 2022-01-04 福建工程学院 Preparation method of antibacterial and anti-fouling regenerated cellulose composite ultrafiltration membrane, composite ultrafiltration membrane and application

Similar Documents

Publication Publication Date Title
CN106621833A (en) Preparation method of ultrafiltration membrane with anti-fouling performance enhanced by nitrogen-doped graphene oxide/TiO2 composite particles
CN102614783B (en) Method for preparing high-flux composite membrane from dopamine-modified nanometer material
Vatanpour et al. Enhancing the permeability and antifouling properties of cellulose acetate ultrafiltration membrane by incorporation of ZnO@ graphitic carbon nitride nanocomposite
CN103463999B (en) Preparation method of ultrathin salt-cutting separation membrane
CN105749766B (en) A kind of Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane
CN108159888A (en) A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance
Chen et al. Fabrication of novel superhydrophilic and underwater superoleophobic hierarchically structured ceramic membrane and its separation performance of oily wastewater
CN109019745A (en) A kind of preparation method improving multi-functional hybridized film particulate load amount
CN105457504A (en) Novel titanium dioxide nano-particle/polymer hybrid membrane and preparation method thereof
Yogarathinam et al. Concentration of whey protein from cheese whey effluent using ultrafiltration by combination of hydrophilic metal oxides and hydrophobic polymer
JP6088932B2 (en) Separation membrane comprising inorganic / organic hybrid compound and method for producing the same
CN111760461B (en) Preparation method of polyvinylidene fluoride mixed matrix membrane
CN106031847B (en) A kind of preparation method for adulterating inorganic/organic nano particle forward osmosis membrane
CN105214511A (en) A kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof
CN107376673B (en) Loaded with TiO2PES ultrafiltration membrane of nanotube and preparation method and application thereof
CN110479109B (en) Preparation method of polyvinylidene fluoride mixed matrix membrane with high flux and strong pollution resistance
CN107126849A (en) A kind of preparation method of hydrophilic polyvinylidene fluoride hybridized film
CN108465377A (en) A kind of preparation method of regenerated cellulose/chitosan composite antibiotic NF membrane
Ma et al. Hydrophilic PAA-g-MWCNT/TiO2@ PES nano-matrix composite membranes: Anti-fouling, antibacterial and photocatalytic
CN112516799A (en) Reverse osmosis membrane and preparation method thereof
Li et al. Preparation and properties of hydrophobic poly (vinylidene fluoride)–SiO2 mixed matrix membranes for dissolved oxygen removal from water
CN111186881A (en) Chitosan modified nano TiO2Preparation method of photocatalytic ultrafiltration membrane
CN103785300A (en) Cellulose acetate and ultrafiltration membrane blending modification method
Gao et al. Superhydrophilic polyethersulfone (PES) membranes with high scale inhibition properties obtained through bionic mineralization and RTIPS
CN106582324A (en) Production method of nano-silver/silica core-shell doped PVDF ultrafilter membrane

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170510

RJ01 Rejection of invention patent application after publication