CN105727763A - Preparation method of fluorine-containing polyamide composite nano-filtration membrane - Google Patents
Preparation method of fluorine-containing polyamide composite nano-filtration membrane Download PDFInfo
- Publication number
- CN105727763A CN105727763A CN201610129859.1A CN201610129859A CN105727763A CN 105727763 A CN105727763 A CN 105727763A CN 201610129859 A CN201610129859 A CN 201610129859A CN 105727763 A CN105727763 A CN 105727763A
- Authority
- CN
- China
- Prior art keywords
- polyamide composite
- fluorine
- nanofiltration membrane
- membrane
- 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.)
- Granted
Links
Classifications
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
Abstract
The invention discloses a preparation method of a fluorine-containing polyamide composite nano-filtration membrane. The preparation method mainly comprises the following steps: preparing a polyether sulfone ultrafiltration basement membrane by adopting a phase transformation method; soaking the membrane in a low-concentration aqueous-phase monomer piperazine and an organic-phase monomer trimesoyl chloride in sequence, and carrying out interfacial polymerization to prepare a polyamide composite nano-filtration membrane; carrying out surface amination on the polyamide composite nano-filtration membrane through surface grafting triethylene tetramine, and modifying hexafluorobutyl methacrylate through Michael addition reaction so as to prepare the fluorine-containing polyamide composite nano-filtration membrane. The preparation method has the advantages as follows: the surface grafting and the Michael addition are combined, so that the process is simple and easy to operate; compared with the traditional polyamide composite nano-filtration membranes, the fluorine-containing polyamide composite nano-filtration membrane prepared through the method has relatively high water flux and separation property under relatively low pressure (0.2 MPa), and shows up favorable anti-pollution characteristic.
Description
Technical field
The preparation method that the present invention relates to a kind of fluorine-containing polyamide composite nanofiltration membrane, belongs to the preparing technical field of composite membrane.
Background technology
Nanofiltration is the separation accuracy a kind of pressure-driven membrane separation technique between reverse osmosis and ultrafiltration, and the aperture of NF membrane is at 0.5-2nm, and its operation pressure is generally 0.3-1.0MPa, and molecular cut off is within the scope of 200-1000.Compared with reverse osmosis, NF membrane has higher water flux under relatively low operation pressure, and divalent ion and organic molecule are had high rejection.NF membrane is widely used in the fields such as bitter desalination, treatment of dyeing wastewater, biochemical preparation and medicine purification.
At present, NF membrane is divided into anisotropic membrane and composite membrane two class by textural classification.Composite membrane is porous basement membrane and covers epilamellar fine and close active layer composition.Wherein, active layer is used for retaining divalent ion or organic molecule, and porous support layer provides the mechanical strength needed for film.The method preparing composite nanometer filtering film mainly includes interfacial polymerization, surface-coated method, surface grafting polymerization method, LBL self-assembly method and bionical Method for bonding etc..The advantages such as wherein interfacial polymerization is simple to operate with it, controllability is strong are widely used in technical field of membrane, and interfacial polymerization can prepare ultra-thin active layer, causes composite membrane under low pressure to have higher selectivity and permeability concurrently.
Preparation of Thin Film Composite Membrane by Interfacial Polymerization Method is that the monomer utilizing two kinds of reactivities significantly high, at two immiscible solvent interface places, polyreactions occurs, thus forming very thin compacted zone on porous basement membrane.Due to solution phase objectionable intermingling in two containing monomer, reaction only occurs in interface, and the polymeric layer therefore generated is very thin, thus causing compound permeability of the membrane and selectivity all to greatly improve.Conventional activated monomer has polyamine, polyhydric alcohol, polyhydric phenols and polynary acyl chlorides etc..Wherein, polyamine, polyhydric alcohol and polyhydric phenols dissolve in aqueous phase, and polynary acyl chlorides then dissolves in organic facies, form the polymeric skins such as polyamide, polyester, polyureas or polyurethane after reaction respectively.Wherein polyamide membrane is modal in Preparation of Thin Film Composite Membrane by Interfacial Polymerization Method, is also industrial film the earliest.
Fouling membrane refers to that the particle in feed liquid, colloid, microorganism, salt etc. are due to the physics between film, chemical action, in film surface or fenestra surface adsorption, deposition and the accumulation at film/water termination place, cause membrane aperture to diminish or block, or cake layer or gel layer is formed on film surface, the resistance to mass tranfer causing separation process increases, and makes the phenomenon of membrane permeation flux continuous decrease.Need film is carried out physical cleaning and Chemical cleaning frequently when fouling membrane is serious, reduce the effective time of film, and cleaning chemical reagent used can damage film itself, shortens the service life of film, adds running cost.Therefore, how effectively to control fouling membrane and become the key issue in current NF membrane field.Prepare the basic method that antipollution NF membrane is reply fouling membrane.
Current tradition is prepared the method for antipollution NF membrane and is mainly surface hydrophilic modification, the pollutant absorption on film surface is stoped by hydrated sheath effect, higher flux recovery can be reached by physical cleaning, but in running, the flux decline of film remains unchanged very serious.Recently, low-surface-energy self-cleaning surface also represents good prospect in pollution-resistant membrane surface construction, can greatly reduce pollutant and film surface reaction forces so that it is can remove from film surface under relatively low hydraulics shear action, therefore can greatly reduce the flux decline of film.Fluorine material is a kind of typical low-surface-energy material, makes substantial progress in marine antifouling coating field.Preparing pollution-resistant membrane field, the methods adopting synthesis fluoropolymer blending and modifying more, but the research on fluorine material modification polyamide NF membrane surface is still less.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of fluorine-containing polyamide composite nanofiltration membrane, this preparation method process is simple to operation, prepared composite nanometer filtering film has higher water flux and separating property under relatively low operation pressure condition, and shows good anti pollution property.
The preparation method of fluorine-containing polyamide composite nanofiltration membrane provided by the invention, including polyether sulfone basement membrane, the preparation of polyamide composite nanofiltration membrane and fluorine-containing polyamide composite nanofiltration membrane, wherein, being prepared by of polyether sulfone basement membrane: polyether sulfone is dissolved in N, dinethylformamide, being configured to containing polyether sulfone mass concentration is the casting solution of 15-18%, 4h is stirred at 60 DEG C, and at 60 DEG C standing and defoaming 4h, it is cooled to casting solution knifing on a glass after room temperature, put into freezing film in 25 DEG C of water-baths, 24h is soaked with deionized water after taking off from glass plate, obtain polyether sulfone basement membrane；Being prepared by of polyamide composite nanofiltration membrane: polyether sulfone basement membrane obtained above is immersed in the piperazine aqueous solution that mass fraction is 0.1%, take out film after 30min and blot the piperazine aqueous solution of surface residual with filter paper, it is immersed in the n-heptane solution of the pyromellitic trimethylsilyl chloride that mass fraction is 0.1% again, take out room temperature in atmosphere after 2min and place 30min, obtain polyamide composite nanofiltration membrane；Being prepared by of fluorine-containing polyamide composite nanofiltration membrane: polyamide nanofiltration membrane obtained above is immersed in the alcoholic solution of the triethylene tetramine that mass fraction is 5.0%, reaction temperature is 60 DEG C, take out after reaction 3h, successively with ethanol and deionized water rinsing, obtain amination polyamide composite nanofiltration membrane；The amination polyamide nanofiltration membrane obtained is immersed in the alcoholic solution of the Hexafluorobutyl mathacrylate that mass fraction is 0.1～0.5%, reaction temperature is 50 DEG C, take out after reaction 12～48h, successively with ethanol and deionized water rinsing, obtain fluorine-containing polyamide composite nanofiltration membrane.
It is an advantage of the current invention that: surface grafting is combined by this preparation method with Michael addition, process is simple to operation, relative to tradition polyamide composite nanofiltration membrane, fluorine-containing polyamide composite nanofiltration membrane prepared by this method is under relatively low operation pressure (0.2MPa), there is higher water flux and separating property, and show good anti pollution property.
Accompanying drawing explanation
Fig. 1 is the variations of flux figure in comparative film filtration bovine serum albumin aqueous solution, humic acid aqueous solution, oil-water emulsion (mass fraction the is 0.1%) process that comparative example is made.
Fig. 2 is that the made fluorine-containing polyamide composite nanofiltration membrane 2 of the embodiment of the present invention 2 filters the variations of flux figure in bovine serum albumin aqueous solution, humic acid aqueous solution, oil-water emulsion (mass fraction is 0.1%) process.
Detailed description of the invention
Below in conjunction with specific embodiment and subordinate list, technical solution of the present invention being described in further detail, the present invention is only explained by described specific embodiment, not in order to limit the present invention.
Embodiment 1, preparing the preparation of fluorine-containing polyamide composite nanofiltration membrane, step is as follows:
Step one, polyether sulfone basement membrane preparation: polyether sulfone is dissolved in N, dinethylformamide, being configured to containing polyether sulfone mass concentration is the casting solution of 15-18%, 4h is stirred at 60 DEG C, and at 60 DEG C standing and defoaming 4h, be cooled to casting solution knifing on a glass after room temperature, put into freezing film in 25 DEG C of water-baths, soak 24h with deionized water after taking off from glass plate, obtain polyether sulfone basement membrane.
Step 2, polyamide composite nanofiltration membrane preparation: polyether sulfone basement membrane step one obtained is immersed in the piperazine aqueous solution that mass fraction is 0.1%, take out film after 30min and blot surface residual aqueous solution with filter paper, it is immersed in the n-heptane solution of the pyromellitic trimethylsilyl chloride that mass fraction is 0.1% again, take out room temperature in atmosphere after 2min and place 30min, obtain polyamide composite nanofiltration membrane.
Step 3, fluorine-containing polyamide composite nanofiltration membrane preparation: polyamide nanofiltration membrane step 2 obtained is immersed in the alcoholic solution of the triethylene tetramine that mass fraction is 5.0%, reaction temperature is 60 DEG C, take out after reaction 3h, successively with ethanol and deionized water rinsing, obtain amination polyamide composite nanofiltration membrane；The amination polyamide nanofiltration membrane obtained is immersed in the alcoholic solution of the Hexafluorobutyl mathacrylate that mass fraction is 0.1%, reaction temperature is 50 DEG C, take out after reaction 24h, successively with ethanol and deionized water rinsing, obtain fluorine-containing polyamide composite nanofiltration membrane, be designated as fluorine-containing polyamide composite nanofiltration membrane 1.
Fluorine-containing polyamide composite nanofiltration membrane 1 obtained by embodiment 1 is 41.5L/ (m at the 0.2MPa water flux operated under pressure2H), to Na2SO4(mass fraction 0.1%) aqueous solution rejection is 78.3%.
Embodiment 2, prepare fluorine-containing polyamide composite nanofiltration membrane, its preparation process is substantially the same manner as Example 1, it is different only in that: in step 3, the amination polyamide nanofiltration membrane obtained is immersed in the alcoholic solution of Hexafluorobutyl mathacrylate, the mass fraction of the alcoholic solution of its Hexafluorobutyl mathacrylate is changed into 0.3% by 0.1%, final prepared fluorine-containing polyamide composite nanofiltration membrane 2.
Fluorine-containing polyamide composite nanofiltration membrane 2 obtained by embodiment 2 is 43.8L/ (m at the 0.2MPa water flux operated under pressure2H), to Na2SO4(mass fraction 0.1%) aqueous solution rejection is 78.8%.Fig. 2 filters the variations of flux figure in bovine serum albumin aqueous solution, humic acid aqueous solution, oil-water emulsion (mass fraction is 0.1%) process for this fluorine-containing polyamide composite nanofiltration membrane 2.
Embodiment 3, prepare fluorine-containing polyamide composite nanofiltration membrane, its preparation process is substantially the same manner as Example 1, it is different only in that: in step 3, the amination polyamide nanofiltration membrane obtained is immersed in the alcoholic solution of Hexafluorobutyl mathacrylate, the mass fraction of the alcoholic solution of its Hexafluorobutyl mathacrylate is changed into 0.5% by 0.1%, final prepared fluorine-containing polyamide composite nanofiltration membrane 3.
Fluorine-containing polyamide composite nanofiltration membrane 3 obtained by embodiment 3 is 41.7L/ (m at the 0.2MPa water flux operated under pressure2H), to Na2SO4(mass fraction 0.1%) aqueous solution rejection is 79.3%.
Embodiment 4, prepare fluorine-containing polyamide composite nanofiltration membrane, its preparation process is substantially the same manner as Example 2, it is different only in that: in step 3, the response time that the amination polyamide nanofiltration membrane obtained is immersed in the alcoholic solution of Hexafluorobutyl mathacrylate by, the mass fraction of the alcoholic solution of its Hexafluorobutyl mathacrylate is changed into 12h by 24h, final prepared fluorine-containing polyamide composite nanofiltration membrane 4.
Fluorine-containing polyamide composite nanofiltration membrane 4 obtained by embodiment 4 is 41.5L/ (m at the 0.2MPa water flux operated under pressure2H), to Na2SO4(mass fraction 0.1%) aqueous solution rejection is 80.3%.
Embodiment 5, prepare fluorine-containing polyamide composite nanofiltration membrane, its preparation process is substantially the same manner as Example 2, it is different only in that: in step 3, the response time that the amination polyamide nanofiltration membrane obtained is immersed in the alcoholic solution of Hexafluorobutyl mathacrylate by, the mass fraction of the alcoholic solution of its Hexafluorobutyl mathacrylate is changed into 48h by 24h, final prepared fluorine-containing polyamide composite nanofiltration membrane 5.
Fluorine-containing polyamide composite nanofiltration membrane 5 obtained by embodiment 5 is 50.0L/ (m at the 0.2MPa water flux operated under pressure2H), to Na2SO4(mass fraction 0.1%) aqueous solution rejection is 76.0%.
Comparative example, a kind of polyamide composite nanofiltration membrane of preparation, preparation process is identical with the step one of embodiment 1 and step 2, finally prepares polyamide composite nanofiltration membrane, is designated as comparative film.
Comparative film prepared by comparative example is 38.2L/ (m at the 0.2MPa water flux operated under pressure2H), to Na2SO4(mass fraction 0.1%) aqueous solution rejection is 79.6%.Fig. 1 is the variations of flux figure in comparative film filtration bovine serum albumin aqueous solution, humic acid aqueous solution, oil-water emulsion (mass fraction the is 0.1%) process that this comparative example is made.
The flux of the polyamide composite nanofiltration membrane that the fluorine-containing polyamide composite nanofiltration membrane that the embodiment of the present invention 1 to 5 prepares prepares with comparative example compares as shown in table 1 with separating property:
Table 1
In sum, the preparation method of a kind of fluorine-containing polyamide composite nanofiltration membrane provided by the invention, mainly adopt phase inversion to prepare polyether sulfone ultrafiltration membranes；Again film is immersed in successively in aqueous phase monomers piperazine and the organic facies monomer pyromellitic trimethylsilyl chloride of low concentration, makes polyamide composite nanofiltration membrane through interfacial polymerization；After adopting surface grafting triethylene tetramine that polyamide composite nanofiltration membrane is carried out surface amination, modify Hexafluorobutyl mathacrylate again through Michael addition reaction, prepare fluorine-containing polyamide composite nanofiltration membrane.It is an advantage of the current invention that: surface grafting is combined by this preparation method with Michael addition, process is simple to operation, by changing fluorochemical monomer (Hexafluorobutyl mathacrylate) liquid quality fraction and fluorochemical monomer response time in preparation process, it is possible to achieve the regulation and control of structure of composite membrane and performance.Relative to tradition polyamide composite nanofiltration membrane, fluorine-containing polyamide composite nanofiltration membrane prepared by this method, under relatively low operation pressure (0.2MPa), has higher water flux and separating property, and shows good anti pollution property.
Although above in conjunction with accompanying drawing, subordinate list, invention has been described; but the invention is not limited in above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is merely schematic; rather than it is restrictive; those of ordinary skill in the art is under the enlightenment of the present invention; without deviating from the spirit of the invention, it is also possible to make many variations, these belong within the protection of the present invention.
Claims (1)
1. the preparation method of a fluorine-containing polyamide composite nanofiltration membrane, it is characterised in that comprise the following steps:
Step one, polyether sulfone basement membrane preparation:
Polyether sulfone is dissolved in N, dinethylformamide, being configured to containing polyether sulfone mass concentration is the casting solution of 15-18%, 4h is stirred at 60 DEG C, and at 60 DEG C standing and defoaming 4h, be cooled to casting solution knifing on a glass after room temperature, put into freezing film in 25 DEG C of water-baths, soak 24h with deionized water after taking off from glass plate, obtain polyether sulfone basement membrane；
Step 2, polyamide composite nanofiltration membrane preparation:
Polyether sulfone basement membrane step one obtained is immersed in the piperazine aqueous solution that mass fraction is 0.1%, take out film after 30min and blot the piperazine aqueous solution of surface residual with filter paper, it is immersed in the n-heptane solution of the pyromellitic trimethylsilyl chloride that mass fraction is 0.1% again, take out room temperature in atmosphere after 2min and place 30min, obtain polyamide composite nanofiltration membrane；
Step 3, fluorine-containing polyamide composite nanofiltration membrane preparation:
Polyamide nanofiltration membrane step 2 obtained is immersed in the alcoholic solution of the triethylene tetramine that mass fraction is 5.0%, and reaction temperature is 60 DEG C, takes out, successively with ethanol and deionized water rinsing, obtain amination polyamide composite nanofiltration membrane after reaction 3h；The amination polyamide nanofiltration membrane obtained is immersed in the alcoholic solution of the Hexafluorobutyl mathacrylate that mass fraction is 0.1～0.5%, reaction temperature is 50 DEG C, take out after reaction 12～48h, successively with ethanol and deionized water rinsing, obtain fluorine-containing polyamide composite nanofiltration membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610129859.1A CN105727763B (en) | 2016-03-07 | 2016-03-07 | A kind of preparation method of fluorine-containing polyamide composite nanofiltration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610129859.1A CN105727763B (en) | 2016-03-07 | 2016-03-07 | A kind of preparation method of fluorine-containing polyamide composite nanofiltration membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105727763A true CN105727763A (en) | 2016-07-06 |
| CN105727763B CN105727763B (en) | 2018-05-22 |
Family
ID=56249234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610129859.1A Active CN105727763B (en) | 2016-03-07 | 2016-03-07 | A kind of preparation method of fluorine-containing polyamide composite nanofiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105727763B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823865A (en) * | 2017-02-23 | 2017-06-13 | 天津大学 | A kind of aromatic polyamide composite reverse osmosis membrane and preparation method for being grafted carbon fluorine class material and aminoglycoside antibiotics |
| CN109012183A (en) * | 2018-07-09 | 2018-12-18 | 天津大学 | A kind of preparation method of the ultra-thin antipollution composite nanometer filtering film of phytic acid assembling |
| CN109569328A (en) * | 2018-12-29 | 2019-04-05 | 安徽智泓净化科技股份有限公司 | A kind of fluorine richness polyamide reverse osmose membrane preparation method |
| CN110437416A (en) * | 2019-08-19 | 2019-11-12 | 美瑞新材料股份有限公司 | A kind of fluorine silication method for preparing polyurethane elastic body of comb shaped structure |
| CN110523303A (en) * | 2019-09-12 | 2019-12-03 | 南京工业大学 | A kind of fluorination polyamide nanofiltration membrane and preparation method thereof |
| CN112058094A (en) * | 2020-09-10 | 2020-12-11 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane and preparation method thereof |
| CN112827368A (en) * | 2021-01-07 | 2021-05-25 | 中化(宁波)润沃膜科技有限公司 | Anti-pollution reverse osmosis membrane and preparation method thereof |
| CN113226527A (en) * | 2018-12-26 | 2021-08-06 | 东丽株式会社 | Composite semipermeable membrane |
| CN114452835A (en) * | 2021-12-30 | 2022-05-10 | 南京工业大学 | Electrically neutral nanofiltration membrane, preparation method and application thereof in small molecule dye wastewater desalination |
| CN114749030A (en) * | 2022-03-29 | 2022-07-15 | 杭州水处理技术研究开发中心有限公司 | Nanofiltration membrane and preparation method and application thereof |
| CN115350590A (en) * | 2022-08-18 | 2022-11-18 | 中原工学院 | Crown ether-based covalent organic framework/polyamide composite nanofiltration membrane as well as preparation method and application thereof |
| CN115364687A (en) * | 2022-08-18 | 2022-11-22 | 天津工业大学 | High-performance nanofiltration membrane and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603580A (en) * | 2018-12-29 | 2019-04-12 | 安徽智泓净化科技股份有限公司 | A kind of preparation method of fluorine surface Modified Cellulose Acetate membrane for Reverse Osmosis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
| CN102179192A (en) * | 2011-03-16 | 2011-09-14 | 天津大学 | Pollution-resistant membrane for filling fluorine-containing amphiphilic surface-modification material and preparation method thereof |
| CN102908914A (en) * | 2012-10-25 | 2013-02-06 | 贵阳时代沃顿科技有限公司 | Composite separating membrane with alloy ultrafiltration layer and preparation method of composite separating membrane |
| US20140251897A1 (en) * | 2011-10-18 | 2014-09-11 | Imperial Innovations Limited | Membranes for separation |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
-
2016
- 2016-03-07 CN CN201610129859.1A patent/CN105727763B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
| CN102179192A (en) * | 2011-03-16 | 2011-09-14 | 天津大学 | Pollution-resistant membrane for filling fluorine-containing amphiphilic surface-modification material and preparation method thereof |
| US20140251897A1 (en) * | 2011-10-18 | 2014-09-11 | Imperial Innovations Limited | Membranes for separation |
| CN102908914A (en) * | 2012-10-25 | 2013-02-06 | 贵阳时代沃顿科技有限公司 | Composite separating membrane with alloy ultrafiltration layer and preparation method of composite separating membrane |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823865B (en) * | 2017-02-23 | 2020-04-10 | 天津大学 | Aromatic polyamide composite reverse osmosis membrane grafted with fluorocarbon material and aminoglycoside antibiotic and preparation method thereof |
| CN106823865A (en) * | 2017-02-23 | 2017-06-13 | 天津大学 | A kind of aromatic polyamide composite reverse osmosis membrane and preparation method for being grafted carbon fluorine class material and aminoglycoside antibiotics |
| CN109012183A (en) * | 2018-07-09 | 2018-12-18 | 天津大学 | A kind of preparation method of the ultra-thin antipollution composite nanometer filtering film of phytic acid assembling |
| CN109012183B (en) * | 2018-07-09 | 2021-02-09 | 天津大学 | Preparation method of ultra-thin anti-pollution composite nanofiltration membrane assembled by phytic acid |
| CN113226527A (en) * | 2018-12-26 | 2021-08-06 | 东丽株式会社 | Composite semipermeable membrane |
| CN113226527B (en) * | 2018-12-26 | 2023-07-18 | 东丽株式会社 | Composite semipermeable membrane |
| CN109569328A (en) * | 2018-12-29 | 2019-04-05 | 安徽智泓净化科技股份有限公司 | A kind of fluorine richness polyamide reverse osmose membrane preparation method |
| CN110437416A (en) * | 2019-08-19 | 2019-11-12 | 美瑞新材料股份有限公司 | A kind of fluorine silication method for preparing polyurethane elastic body of comb shaped structure |
| CN110437416B (en) * | 2019-08-19 | 2021-08-10 | 美瑞新材料股份有限公司 | Preparation method of fluorosilicated polyurethane elastomer with comb-shaped structure |
| CN110523303A (en) * | 2019-09-12 | 2019-12-03 | 南京工业大学 | A kind of fluorination polyamide nanofiltration membrane and preparation method thereof |
| CN110523303B (en) * | 2019-09-12 | 2021-11-02 | 南京工业大学 | Fluorinated polyamide nanofiltration membrane and preparation method thereof |
| CN112058094A (en) * | 2020-09-10 | 2020-12-11 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane and preparation method thereof |
| CN112058094B (en) * | 2020-09-10 | 2021-04-30 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane and preparation method thereof |
| CN112827368A (en) * | 2021-01-07 | 2021-05-25 | 中化(宁波)润沃膜科技有限公司 | Anti-pollution reverse osmosis membrane and preparation method thereof |
| CN112827368B (en) * | 2021-01-07 | 2023-08-11 | 中化(宁波)润沃膜科技有限公司 | Anti-pollution reverse osmosis membrane and preparation method thereof |
| CN114452835A (en) * | 2021-12-30 | 2022-05-10 | 南京工业大学 | Electrically neutral nanofiltration membrane, preparation method and application thereof in small molecule dye wastewater desalination |
| CN114452835B (en) * | 2021-12-30 | 2024-01-09 | 南京工业大学 | Neutral nanofiltration membrane, preparation method and application thereof in small-molecule dye wastewater desalination |
| CN114749030A (en) * | 2022-03-29 | 2022-07-15 | 杭州水处理技术研究开发中心有限公司 | Nanofiltration membrane and preparation method and application thereof |
| CN115350590A (en) * | 2022-08-18 | 2022-11-18 | 中原工学院 | Crown ether-based covalent organic framework/polyamide composite nanofiltration membrane as well as preparation method and application thereof |
| CN115364687A (en) * | 2022-08-18 | 2022-11-22 | 天津工业大学 | High-performance nanofiltration membrane and preparation method and application thereof |
| CN115350590B (en) * | 2022-08-18 | 2024-03-01 | 中原工学院 | Crown ether group covalent organic framework/polyamide composite nanofiltration membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105727763B (en) | 2018-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105727763A (en) | Preparation method of fluorine-containing polyamide composite nano-filtration membrane | |
| US11433358B2 (en) | Composite reverse osmosis membrane and preparation method thereof | |
| WO2018120476A1 (en) | Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof | |
| CN110314556B (en) | High-flux nanofiltration membrane for selectively removing hydrophobic endocrine disruptors and preparation method thereof | |
| US20160151748A1 (en) | Reverse osmosis or nanofiltration membranes and method for production thereof | |
| WO2012102678A1 (en) | A forward osmosis membrane | |
| CN104474925A (en) | Preparation method of composite high-water-flux polyamide reverse-osmosis membrane | |
| CN111185105B (en) | High-performance polyamide composite separation membrane based on biopolymer-contaminated basement membrane and preparation method thereof | |
| WO2019153946A1 (en) | High-performance forward osmosis membrane, preparation method therefor and application thereof | |
| CN110327796B (en) | Preparation method of zwitterion-modified polypiperazine amide nanofiltration membrane | |
| CN109847597B (en) | High-flux high-desalination reverse osmosis membrane and preparation method thereof | |
| CN105148750A (en) | Method for modifying surface of polyamide composite film | |
| CN106943891B (en) | Pollution-resistant composite membrane, preparation method thereof and oil-water emulsion separation method | |
| CN114288876B (en) | Preparation method of crown ether functionalized nanofiltration membrane for extracting lithium from magnesium-lithium mixed solution | |
| CN110548420B (en) | Preparation method of zero-flux attenuation chemical heterogeneous hydrogel ultrafiltration membrane | |
| CN110743383B (en) | Modification method for improving permeation flux of polyamide composite membrane | |
| CN114870641B (en) | Piperazinyl primary positively charged nanofiltration membrane and preparation method thereof | |
| CN108211794B (en) | High-selectivity hollow fiber desalting membrane and preparation method thereof | |
| Vainrot et al. | Membranes in desalination and water treatment | |
| CN102179192A (en) | Pollution-resistant membrane for filling fluorine-containing amphiphilic surface-modification material and preparation method thereof | |
| EP1301256A2 (en) | Method for modifying membrane rejection characteristics | |
| KR102041657B1 (en) | Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane | |
| CN110624419B (en) | Reverse osmosis membrane environment-friendly recycling method | |
| CN112973467B (en) | Preparation method of composite nanofiltration membrane and composite nanofiltration membrane | |
| KR102067861B1 (en) | Composition for preparing reverse osmosis membrane, method for preparing reverse osmosis membrane using the same, and reverse osmosis membrane and water treatment module |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 300350 Haijing garden, Haihe Education Park, Jinnan, Tianjin, 135, Tianjin University. Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
|
| CP02 | Change in the address of a patent holder |