CN105536556A - Separation membrane with oleophobic performance and application thereof - Google Patents
Separation membrane with oleophobic performance and application thereof Download PDFInfo
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- CN105536556A CN105536556A CN201511015393.4A CN201511015393A CN105536556A CN 105536556 A CN105536556 A CN 105536556A CN 201511015393 A CN201511015393 A CN 201511015393A CN 105536556 A CN105536556 A CN 105536556A
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- diffusion barrier
- oleophobic
- oleophobic properties
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- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention relates to a separation membrane with oleophobic performance. A perfluoroalkyl group-enriched compound coating layer is modified on the surface of a porous base membrane in an immersing or spraying manner; due to curing treatment, the oleophobic performance of the separation membrane is improved; the separation membrane can be applied to such gas and liquid treatment fields as air filtration, membrane distillationdesalination and oil-water separation, so that the anti-pollution performance is improved.
Description
Technical field
The present invention relates to a kind of diffusion barrier with oleophobic properties, be rich in all-fluoroalkyl compound coating by immersion or spraying method in the modification of porous membrane surface.Can be used for gas and the liquid handling fields such as air filtration, Membrane Materials desalination, water-oil separating.
Background technology
Oleophobic surface refers generally to be greater than 90 ° with the contact angle of oil, and oil droplet can not, in the stable stop of oleophobic surface, be easy to not stay any vestige from tumbling on the surface.Oleophobic surface is with a wide range of applications in fields such as antifouling, anticorrosion, liquid transportings.Prepare super oleophobic surface, usually have two kinds of methods: one is in surface roughness, modify the perfluorochemical with pole low surface free energy; Two is directly at fluorine-containing material surface design coarse structure.Patent CN200910009954.8, CN201210435983.2, CN201310309217.6 and CN201310224027.4 etc. report the preparation method of oleophobic modification diffusion barrier, method for generating oleophobic surface is all combined with at least two steps, comprises the combination of the surface light lithography of face coat method and complexity, plasma-deposited etc. with fluorohydrocarbon.Patent CN101630324A forms interlaced transverse and longitudinal fine streaks by fine finishining at material surface, thus builds oleophobic surface.Described oleophobic surface construction step is complicated, and process conditions are harsher, cannot large-scale promotion.Therefore develop that a kind of preparation method is simple, cost is low, be applicable to the oleophobic method of modifying of multiple matrix surface is very important.
Summary of the invention
The object of this invention is to provide a kind of diffusion barrier with oleophobic properties, be rich in all-fluoroalkyl compound coating by immersion or spraying method in the modification of porous membrane surface.This preparation method's technique is simple, is suitable for suitability for industrialized production; Apply oleophobic diffusion barrier provided by the invention and carry out purification of air and membrane filtration, the antipollution effect of film can be improved.
The invention provides following technical scheme:
There is a diffusion barrier for oleophobic properties, it is characterized in that,
A () has the basement membrane of loose structure.
B () deposits at basement membrane single or double and is rich in all-fluoroalkyl compound coating.
All-fluoroalkyl compound coating described in (c) according to AATCC118 method of testing measure be at least 6 oil resistant and pollutant ability.
Wherein, the described diffusion barrier with oleophobic properties, is characterized in that, fluoroalkyl coating layer thickness 0.1 nanometer-10 nanometer.
Wherein, the described diffusion barrier with oleophobic properties, it is characterized in that, analyzing its fluorine element content containing all-fluoroalkyl compound coating surface X-ray photoelectron spectroscopic analysis (XPS) is 30-80%, and fluorine element content does not change with diffusion barrier service time.
Wherein, the described diffusion barrier with oleophobic properties, it is characterized in that: all-fluoroalkyl compound coating is rich in the solution of fluoroalkyle compound by being immersed in by porous basement membrane single or double one or many, maybe the solution one or many being rich in all-fluoroalkyl compound is sprayed on porous basement membrane single or double and formed; The oleophobic property of porous basement membrane can be promoted by solidification process, oily contact angle is promoted significantly.
Wherein, described all-fluoroalkyl compound coating, is characterized in that: described one or many soaks or spraying, comprises 1-100 time, and immersion or spray time are 1 second-60min.Solidification process treatment temperature is 20-200
oc, the solidification processing time is 1 second-20 hours.
Wherein, the described diffusion barrier with oleophobic properties, is characterized in that: porous basement membrane base material is selected from but is not limited to macromolecule, inorganic ceramic, glass fibre or metal porous net etc., and wherein membrane surface bore dia is 1 nanometer-100 microns.
Wherein, described porous basement membrane base material, it is characterized in that: described macromolecule member material is selected from but is not limited to polyolefin, polyamide, polyester, polysulfones, polyethers, Merlon, PETG (PET), Kynoar (PVDF), vinylidene fluoride homopolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylene, skewed segregation, Kynoar-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polystyrene, polyvinyl chloride, polysulfones, polyether sulfone, polyacrylonitrile, one or more in cellulosic polymer, the porous web of aluminium oxide, zirconia, titanium oxide and silicon oxide ceramics film, glass fibre membrane and metal and metal oxide and porous sintered plate.
Wherein, described is rich in all-fluoroalkyl compound, it is characterized in that: be rich in perfluoroalkyl (C in its molecular skeleton chain or side chain
nf
2n+1, n>=3) compound, include but not limited to S-triazines, amide-type, aromatic polycarboxylic acids class, the aziridine type, silicon-fluorine polymer thing class, polyacrylate class, polyurethanes etc.
Wherein, described is rich in all-fluoroalkyl compound solution, it is characterized in that: all-fluoroalkyl compound concentration is 0.01-10wt.%, conventional solvent is for can dissolve all-fluoroalkyl compound, but do not destroy the organic solvent of porous basement membrane, include but not limited to alcohols, alkane solvents, ester class, DMF, DMSO, DMAC etc.One or more having in ethanol, isopropyl alcohol, n-butanol, isoamyl alcohol, 1-Methoxy-2-propyl acetate, n-butyl acetate, n-hexane etc. conventional.
Wherein, the described diffusion barrier with oleophobic properties, is characterized in that, can gas and the liquid handling field such as application of air filtration, Membrane Materials desalination, water-oil separating.
Detailed description of the invention
In case study on implementation below, the invention will be further elaborated, but the present invention is not limited thereto.
Case study on implementation 1-2
PVDF nano fibrous membrane being immersed in concentration is 0.1wt.%1H, 1H, 2H, 15min in 2H-perfluoro decyl triethoxysilane (FAS) solution, at room temperature dry after repeating immersion 8 times, take out after being put in 130 DEG C of heat treatment 1h subsequently, obtain the stable film surface with fuel shedding quality.The contact angle of oleophobic Modified Membrane to soybean oil reaches 110 °.Oleophobic Modified Membrane is applied to the field such as air filtration and Membrane Materials desalination respectively.
(1) oleophobic Modified Membrane being used for air filtration, is 100% to the removal efficiency of PM2.5.
(2) after oleophobic Modified Membrane being carried out hot-pressing processing, retain the contact angle of layer to water and reach 140 °, carry out sea water desalting for Membrane Materials feed liquid, when temperature difference is 40 degree, water flux is 30LMH, and salt-stopping rate is 99.9%.Composite membrane still can keep efficient salt rejection rate and water vapour flux in the running time range reaching 20 hours.
Case study on implementation 3
PET non-woven fabrics being immersed in concentration is 1min in the fluoromethacrylates solution of 10wt.%, after drying, obtains the stable film surface with fuel shedding quality, reaches 160 ° to the contact angle of hexane under room temperature.Oleophobic Modified Membrane is used for air filtration, is 100% to the removal efficiency of PM2.5.
Case study on implementation 4-5
PP nano fibrous membrane being immersed in concentration is 1min in the fluorinated acrylamide acid solution of 0.5wt.%, takes out after 80 DEG C of heat treatment 10h, obtains the stable film surface with fuel shedding quality.The contact angle of oleophobic Modified Membrane to soybean oil reaches 100 °.
(1) oleophobic Modified Membrane being used for air filtration, is 100% to the removal efficiency of PM2.5.
(2) carry out sea water desalting for Membrane Materials feed liquid, when temperature difference is 50 degree, water flux is 100LMH, and salt-stopping rate is 99.9%.
Case study on implementation 6
By silicon oxide ceramics film soak 0.1wt.% fluorinated siloxane (fluoridizing POSS) solution in 10 minutes, soaking number of times is 100 times, by film at room temperature dry solidification after immersion completes, obtain the stable silicon oxide ceramics film surface with fuel shedding quality, 120 ° are reached to the contact angle of hexane.
Case study on implementation 7
Adopt spraying method that fluorinated siloxane (FAS) solution of 0.2wt.% is applied to glass fibre membrane surface, spray time is 30s, spraying number of times is 2 times, after having sprayed, film is taken out after 80 DEG C of heat treatment 20h, obtain the stable glass fibre membrane with fuel shedding quality, 150 ° are reached to the contact angle of soybean oil.
It should be noted last that, above detailed description of the invention is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to example to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. there is a diffusion barrier for oleophobic properties, it is characterized in that,
A () has the basement membrane of loose structure;
B () deposits at basement membrane single or double and is rich in all-fluoroalkyl compound coating;
All-fluoroalkyl compound coating described in (c) according to AATCC118 method of testing measure be at least 6 oil resistant and pollutant ability.
2. the diffusion barrier with oleophobic properties according to claim 1, is characterized in that, fluoroalkyl coating layer thickness 0.1 nanometer-10 nanometer.
3. the diffusion barrier with oleophobic properties according to claim 1, it is characterized in that, analyzing its fluorine element content containing all-fluoroalkyl compound coating surface X-ray photoelectron spectroscopic analysis (XPS) is 30-80%, and fluorine element content does not change with diffusion barrier service time.
4. the diffusion barrier with oleophobic properties according to claim 1, it is characterized in that: all-fluoroalkyl compound coating is rich in the solution of fluoroalkyle compound by being immersed in by porous basement membrane single or double one or many, maybe the solution one or many being rich in all-fluoroalkyl compound is sprayed on porous basement membrane single or double and formed; The oleophobic property of porous basement membrane can be promoted by solidification process, oily contact angle is promoted significantly.
5. the diffusion barrier with oleophobic properties according to claim 4, it is characterized in that: described all-fluoroalkyl compound coating one or many soaks or spraying, comprise 1-100 time, immersion or spray time are 1 second-60min, and solidification process treatment temperature is 20-200
oc, the solidification processing time is 1 second-20 hours.
6. the diffusion barrier with oleophobic properties according to claim 1,2,3,4 or 5, it is characterized in that: porous basement membrane base material is selected from but is not limited to macromolecule, inorganic ceramic, glass fibre or metal porous net etc., and wherein membrane surface bore dia is 1 nanometer-100 microns.
7. the diffusion barrier with oleophobic properties according to claim 6, it is characterized in that: described macromolecule member material is selected from but is not limited to polyolefin, polyamide, polyester, polysulfones, polyethers, Merlon, PETG (PET), Kynoar (PVDF), vinylidene fluoride homopolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylene, skewed segregation, Kynoar-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polystyrene, polyvinyl chloride, polysulfones, polyether sulfone, polyacrylonitrile, one or more in cellulosic polymer, the porous web of aluminium oxide, zirconia, titanium oxide and silicon oxide ceramics film, glass fibre membrane and metal and metal oxide and porous sintered plate.
8., by the diffusion barrier with oleophobic properties described in claim 1,2,3 or 5, it is characterized in that: described in be rich in its molecular skeleton chain of all-fluoroalkyl compound or side chain and be rich in perfluoroalkyl (C
nf
2n+1, n>=3) compound, include but not limited to S-triazines, amide-type, aromatic polycarboxylic acids class, the aziridine type, silicon-fluorine polymer thing class, polyacrylate class, polyurethanes etc.
9. by the diffusion barrier with oleophobic properties described in claim 1,2,3 or 5, it is characterized in that: described all-fluoroalkyl compound concentration is 0.01-10wt.%, conventional solvent is for can dissolve all-fluoroalkyl compound, but do not destroy the organic solvent of porous basement membrane, include but not limited to alcohols, alkane solvents, ester class, DMF, DMSO, DMAC etc., one or more having in ethanol, isopropyl alcohol, n-butanol, isoamyl alcohol, 1-Methoxy-2-propyl acetate, n-butyl acetate, n-hexane etc. conventional.
10., by the diffusion barrier with oleophobic properties according to claim 1, it is characterized in that, can gas and the liquid handling field such as application of air filtration, Membrane Materials desalination, water-oil separating.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106624086A (en) * | 2017-01-06 | 2017-05-10 | 长春理工大学 | Metal-based in-water oil-repellent surface and machining method thereof |
| CN107158953A (en) * | 2017-07-18 | 2017-09-15 | 中国科学院生态环境研究中心 | A kind of preparation method of membrane distillation nano wire hydrophobic membrane |
| CN108786478A (en) * | 2018-05-04 | 2018-11-13 | 河南工程学院 | The preparation method of membrane distillation composite membrane |
| CN109173754A (en) * | 2018-08-23 | 2019-01-11 | 师帅帅 | A kind of high-salt wastewater processing fluorine silicon fiml and preparation method thereof |
| CN109731554A (en) * | 2019-03-12 | 2019-05-10 | 海安县中丽化工材料有限公司 | A kind of administering method of oily waste water |
| CN109731553A (en) * | 2019-03-12 | 2019-05-10 | 海安县中丽化工材料有限公司 | A kind of TiO2The preparation method of@Mofs modified glass-fiber film |
| CN110270136A (en) * | 2019-07-16 | 2019-09-24 | 黑龙江东方学院 | A kind of preparation method and application of hydrophilic functions film |
| CN111511460A (en) * | 2017-12-27 | 2020-08-07 | 住友电气工业株式会社 | Filtering membrane for treating oily wastewater and filtering module for treating oily wastewater |
| KR20200107121A (en) * | 2019-03-06 | 2020-09-16 | 주식회사 엘지화학 | Gas separation membrane, gas separation membrane module comprising the same and preparation method for the same |
| CN113663528A (en) * | 2021-08-12 | 2021-11-19 | 中国石油大学(华东) | Preparation method of fluorine-containing oil-water separation membrane with high oil pollution resistance and stability |
| CN113754472A (en) * | 2021-08-10 | 2021-12-07 | 浙江零零零环境科技有限公司 | Hydrophobic and oleophobic treatment method for silicon carbide ceramic membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106624086A (en) * | 2017-01-06 | 2017-05-10 | 长春理工大学 | Metal-based in-water oil-repellent surface and machining method thereof |
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| CN108786478A (en) * | 2018-05-04 | 2018-11-13 | 河南工程学院 | The preparation method of membrane distillation composite membrane |
| CN109173754A (en) * | 2018-08-23 | 2019-01-11 | 师帅帅 | A kind of high-salt wastewater processing fluorine silicon fiml and preparation method thereof |
| KR20200107121A (en) * | 2019-03-06 | 2020-09-16 | 주식회사 엘지화학 | Gas separation membrane, gas separation membrane module comprising the same and preparation method for the same |
| KR102637321B1 (en) * | 2019-03-06 | 2024-02-15 | 주식회사 엘지화학 | Gas separation membrane, gas separation membrane module comprising the same and preparation method for the same |
| CN109731553A (en) * | 2019-03-12 | 2019-05-10 | 海安县中丽化工材料有限公司 | A kind of TiO2The preparation method of@Mofs modified glass-fiber film |
| CN109731554A (en) * | 2019-03-12 | 2019-05-10 | 海安县中丽化工材料有限公司 | A kind of administering method of oily waste water |
| CN110270136A (en) * | 2019-07-16 | 2019-09-24 | 黑龙江东方学院 | A kind of preparation method and application of hydrophilic functions film |
| CN113754472A (en) * | 2021-08-10 | 2021-12-07 | 浙江零零零环境科技有限公司 | Hydrophobic and oleophobic treatment method for silicon carbide ceramic membrane |
| CN113663528A (en) * | 2021-08-12 | 2021-11-19 | 中国石油大学(华东) | Preparation method of fluorine-containing oil-water separation membrane with high oil pollution resistance and stability |
| CN113663528B (en) * | 2021-08-12 | 2023-10-27 | 中国石油大学(华东) | Preparation method of fluorine-containing oil-water separation membrane with high oil pollution resistance and stability |
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