CN107081075A - A kind of preparation method and applications of selective water-oil separating Dynamic Membrane - Google Patents
A kind of preparation method and applications of selective water-oil separating Dynamic Membrane Download PDFInfo
- Publication number
- CN107081075A CN107081075A CN201710346237.9A CN201710346237A CN107081075A CN 107081075 A CN107081075 A CN 107081075A CN 201710346237 A CN201710346237 A CN 201710346237A CN 107081075 A CN107081075 A CN 107081075A
- Authority
- CN
- China
- Prior art keywords
- zinc
- dynamic membrane
- membrane
- water
- oil separating
- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- 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
- B01D67/0039—Inorganic 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
- B01D69/14—Dynamic membranes
-
- 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
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- 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
-
- 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
Abstract
The invention belongs to chemical separating field of material technology, it is related to water-oil separationg film, more particularly to a kind of preparation method and applications of selective water-oil separating Dynamic Membrane.Zinc acetate is added in absolute ethyl alcohol by the present invention first, it is heated to reflux that zinc colloidal sol is made, basement membrane is impregnated into zinc colloidal sol again, high annealing obtains the perforated substrate film of coating zinc oxide seed, then itself and zinc acetate pH adjusting agent solution are subjected to hydro-thermal reaction, washing obtains the porous diffusion barrier of zinc oxide precoated shet after drying；Using the influence of the surface related defects of precoated shet zinc oxide, oxygen defect is removed in atmosphere of hydrogen or oxygen defect is obtained in oxygen atmosphere, super-hydrophobic and ultra-hydrophilic surface is obtained respectively, the problem of solving the wetting poor selectivity that water-oil separationg film is present.According to the selective water-oil separating Dynamic Membrane of wetting produced by the present invention, water-oil separating is can be applied to, and energy repeated reproducibility is used.Manufacture craft of the present invention is simple, non-secondary pollution and noxious material discharge, energy-conservation, is applicable industrialized production.
Description
Technical field
The invention belongs to chemical separating field of material technology, it is related to water-oil separationg film, more particularly to a kind of selective profit
Separate the preparation method and applications of Dynamic Membrane.
Background technology
As a kind of high pollution material, oily waste water and paper waste, dyeing waste water and referred to as three big industrial wastewaters, it is arranged
High-volume big and wide material sources, serious pollution is caused to ecological environment.The source of oily waste water mainly includes：(1), Oil Refining Industry,
The oily waste water that the high oil consumption industry such as textile industry, grocery trade is produced；(2), the oily waste water that oil exploitation and transportation are produced；
(3), frequently oil leak event, makes substantial oil be leaked in environment, forms oil-polluted water.At present, China will contain greasy dirt
The improvement of water and recycling, are classified as the important process that country carries out recycling economy, built a conservation-minded society.In oil-polluted water
Oil product efficiently separating and reclaiming, and will be fundamental way that it will be disposed from now on, carries out water-oil separating and corresponding control method
Research is particularly important.
The essence of Selective Separation profit is water-oil separating material interface problem, passes through microstructure design and superficiality
It can optimize, obtain the water-oil separationg film of super wetting property, undoubtedly improve its maximally effective means of water-oil separating performance.It is super thin
The water-oil separating at water/super oleophylic interface is the process based on the Selective Separation oil product from water body, and its mechanism is " oil is removed ", right
The oil product for being more than water in density has preferable separating effect, but is difficult oil product and oil-in-water emulsion of the separating floating on water.
The water-oil separating at super hydrophilic/superoleophobic interface is the process based on the Selective Separation water quality from oil, and its mechanism is " water removal ",
The oil product of floating on the water can be efficiently separated, but is difficult separation for the larger oil product of density and water-in-oil emulsion.Therefore, film point
Key problem from processing oily waste water is the problem of improving water-oil separating selectivity and improve interface infiltrating.
In actual oil water separation process, the problems such as fouling membrane is seriously and membrane module is expensive limits the wide of membrane technology
General application.The matter of utmost importance that water-oil separating film process oily waste water is faced is：Solve fouling membrane caused by low separation efficiency and
The problem of reusability is poor.While the bionical preparation of research water-oil separationg film, it is also contemplated that fouling membrane and film regenerability
The problem of.Prevent at present water-oil separating fouling membrane method include to the surface treatment of membrane material (including surface grafting, crosslinking,
Etching, surface spraying etc.) and oil-water mixture pretreatment (including pre-filtering, heat treatment plus compounding ingredient plus adsorbent and steady
Determine agent etc.).Membrane material surface treatment would generally change wellability, charge and surface texture of film etc., and then influence profit point
From efficiency；And oily waste liquor preprocessing process is then complex, it can also bring that cost is high, efficiency is low, easy secondary pollution problems.
As a kind of membrane technology of special shape, Dynamic Membrane contains organic or inorganic material using porous media filtering
Solution, a level filming layer, i.e., dynamic film layer are deposited or assemble in dielectric surface.Dynamic Membrane can mitigate the fouling membrane of basement membrane, drop
The low price of membrane module, and with good permeability and rejection effect.Once water-oil separationg film surface is contaminated, secondary filming
Easily remove, it is possible to film forming again.Compared with fixed film, dynamic water-oil separationg film has that cost is low, flux is big, interception capacity
By force, the advantages of preparing simple and easy to clean.Therefore, the film dirt that oil water separation process is run into can be solved by constructing Dynamic Separation film
Dye problem, and film group price and prolonging service lifetime of film can be reduced.
The content of the invention
For above-mentioned the deficiencies in the prior art, it is an object of the present invention to disclose a kind of selective profit
Separate the preparation method of Dynamic Membrane.
The present invention is using porous nethike embrane as basement membrane, and micro nano structure zinc oxide is time filming, constructs dynamic water-oil separationg film, profit
With the reproducibility of dynamic layer, the membrane pollution problem in oil water separation process is effectively solved.The present invention utilizes precoated shet zinc oxide
The influence of surface related defects, oxygen defect is removed in atmosphere of hydrogen or oxygen defect is obtained in oxygen atmosphere, is surpassed respectively
Hydrophobic and ultra-hydrophilic surface, solves prior art and prepares the shortcoming that water-oil separating membrane material soaks poor selectivity, expand oil
Water separation membrane material application in water-oil separating.
A kind of preparation method of selective water-oil separating Dynamic Membrane, comprises the following steps：
a）Add 0.001~0.1mol by every 100mL absolute ethyl alcohols, zinc acetate is added to nothing by preferably 0.1mol zinc acetate meter
In water-ethanol, strong stirring is to dissolving, and gained zinc acetate ethanol solution is at 60~80 DEG C, and flow back 3h at preferably 60 DEG C, obtains milky white
Color zinc colloidal sol；
b）Add 5 by basement membrane every square centimeter~10mL zinc colloidal sols based on, basement membrane is immersed in 10s in zinc colloidal sol, at 60~120 DEG C,
It is preferred that at 60 DEG C, drying 10~40min, preferably 20min, immersion 3~9 times is repeated, at 200~350 DEG C, is moved back at preferably 250 DEG C
The fire preferred 15min of 15~45min, obtain the perforated substrate film of coating zinc oxide seed, wherein, the basement membrane is copper mesh, titanium dioxide
One or more kinds of combinations in silica fibre film, stainless (steel) wire, cotton, nylon cloth, preferably silicon dioxide fibrous membrane；
c）By 0.01~0.1mol/L, preferably 0.01mol/L zinc acetate aqueous solutions, and 0.01~0.2mol/L, preferably
0.01mol/L pH adjusting agent aqueous solutions, it is isometric well mixed, obtain zinc acetate pH adjusting agent mixed solution；By every square centimeter
Plus 10mL zinc acetate pH adjusting agent mixed solution meters, the perforated substrate film and zinc acetate pH adjusting agent of coating zinc oxide seed is molten
Liquid is added in polytetrafluoroethyllining lining reactor, and 6~16h is reacted at 60~120 DEG C, 2~5 are washed with deionized after taking-up
Secondary, 4~8h of air drying obtains the porous diffusion barrier of zinc oxide precoated shet, wherein the pH adjusting agent be ammonium chloride, ammonium fluoride,
One or more combinations in ammonium nitrate, hexamethylene tetramine, ammoniacal liquor, urea etc., preferably hexamethylene tetramine；
d）It is passed through by every square centimeter based on 9~20sccm of flow hydrogen, the porous diffusion barrier of zinc oxide precoated shet is placed on
In tube furnace, 1~6h, preferably 3h are reacted at 200~400 DEG C, preferably 300 DEG C, the zinc oxide precoating with ultra-hydrophobicity is obtained
The porous separation Dynamic Membrane of layer；
e）By the oxymeter every square centimeter for being passed through 5~25sccm of flow, the porous diffusion barrier of zinc oxide precoated shet is placed on
In tube furnace, 1~6h, preferably 3h are reacted at 300~400 DEG C, preferably 300 DEG C, the zinc oxide precoating with super hydrophilicity is obtained
The porous separation Dynamic Membrane of layer.
Selective water-oil separating Dynamic Membrane is soaked according to made from the method for the invention, by time with wetting selectivity
Filming is formed in membrane surface growth in situ, wherein, the basement membrane is porous fibre nethike embrane, and described filming is with wetting choosing
The zinc oxide of selecting property, the thickness of secondary filming is 200~2000nm.
Another object of the present invention is, selective water-oil separating is soaked according to made from the method for the invention and is moved
State film, can be applied to water-oil separating.
Third object of the present invention is, discloses the renovation process of selective water-oil separating Dynamic Membrane.According to this hair
There is the porous separation Dynamic Membrane of the zinc oxide precoated shet of ultra-hydrophobicity and with super hydrophilicity made from bright methods described
Zinc oxide precoated shet porous separation Dynamic Membrane, contaminated after multiple water-oil separating application, renovation process is as follows：
Porous separation Dynamic Membrane by contaminated zinc oxide precoated shet every square centimeter is soaked polluted membrane with based on 10mL diluted acids
In 0.01~0.1mol/L dilute acid soln, taken out after 1~3h, deionized water dries 1~5h at washing 3~6 times, 60 DEG C；
Preparation process a~d is repeated, or repeats preparation process a~c-e, you can regeneration.
The present invention removes oxygen defect and in oxygen atmosphere using the influence of zinc oxide surface related defects in atmosphere of hydrogen
Middle acquisition oxygen defect, obtains super-hydrophobic and ultra-hydrophilic surface respectively, solves asking for the wetting poor selectivity that water-oil separationg film is present
Topic.Zinc oxide using porous fibrous material as basement membrane, with wetting selectivity is time filming, constructs dynamic water-oil separationg film, can
The membrane pollution problem of oil water separation process is effectively solved, and Making programme is simple, cost is low, has in water-oil separating field
Preferable application prospect.
Beneficial effect
There is the dynamic membrane preparation method of the selective water-oil separating of wetting the invention discloses a kind of, have the following advantages that：（1）Profit
Wet selective water-oil separating Dynamic Membrane only relies on Action of Gravity Field and completes to separate with capillary effect in oil water separation process
Journey, in addition to the material transmission a small amount of energy of energy consumption, without additional energy, with the advantage for saving the energy.（2）Soak Selective Separation
Dynamic Membrane is without extra chemical modifier in preparation process, and preparation technology is simple, it is to avoid the conventional modified chemistry examination existed
Agent uses problem, non-secondary pollution, the characteristics of with environmental protection.（3）Water-oil separationg film has selective wetting, by using
The wetting selectivity of zinc oxide, super-hydrophobic and ultra-hydrophilic surface can be obtained respectively, solve traditional water-oil separationg film wetting selection
Then the shortcoming of property difference and low separation efficiency, extends the application of water-oil separating.（4）Water-oil separating Dynamic Membrane, using secondary
The regenerability of film, can effectively solve the membrane pollution problem of traditional water-oil separationg film, extend the service life of seperation film, improve
Water-oil separating membrane separation efficiency.（5）Raw material needed for preparing water-oil separationg film are cheap and easy to get, and manufacture craft letter
It is single, do not result in secondary pollution and noxious material discharge, it is easy to accomplish, it is adaptable to extensive a wide range of production.
Embodiment
With reference to embodiment, the present invention is described in detail, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited in following examples.
Embodiment 1
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.1mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring is to dissolving, and gained zinc acetate ethanol solution exists
Flow back 3h at 60 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of silicon dioxide fibrous membrane is immersed in 10s in 50mL zinc colloidal sols, 20min, weight are dried at 60 DEG C
Soak 5 times again, anneal 15min at 350 DEG C, obtains the silicon dioxide fibrous membrane of coating zinc oxide seed；
c）The mixed solution that 80mL concentration is 0.01mol/L zinc acetates and concentration is 0.01mol/L hexamethylene tetramines is prepared,
The mixed solution of the silicon dioxide fibrous membrane of coating zinc oxide seed and 80mL is added to the reactor of polytetrafluoroethyllining lining
In, react and be washed with deionized after 6h, taking-up 3 times at 60 DEG C, air drying 4h obtains silicon dioxide fibre Dynamic Membrane；
d）Silicon dioxide fibre Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 9sccm is passed through, is reacted at 200 DEG C
6h, is obtained with ultra-hydrophobicity silicon dioxide fibre Dynamic Membrane；
e）Silicon dioxide fibre Dynamic Membrane is placed in tube furnace, the oxygen that flow is 10sccm is passed through, is reacted at 300 DEG C
3h, obtains the silicon dioxide fibre Dynamic Membrane with super hydrophilicity.
Renovation process：To contaminated super hydrophilic and superhydrophobic silica fiber Dynamic Membrane after repeatedly water-oil separating
It is immersed in the dilute hydrochloric acid solution that 100mL concentration is 0.01mol/L, is taken out after 1h, deionized water is dried at washing 3 times, 60 DEG C
1h；Preparation process a~e is repeated, the selective Dynamic Membrane of wetting of regeneration is obtained.
Embodiment 2
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.1mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring is to dissolving, and gained zinc acetate ethanol solution exists
Flow back 3h at 80 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of silicon dioxide fibrous membrane is immersed in 10s in 50mL zinc colloidal sols, 10min, weight are dried at 80 DEG C
Soak 5 times again, anneal 15min at 200 DEG C, obtains the silicon dioxide fibrous membrane of coating zinc oxide seed；
c）It is 0.01mol/L zinc acetates and the mixed solution that concentration is 0.01mol/L ammonium chlorides to prepare 80mL concentration, will be coated
The silicon dioxide fibrous membrane of zinc oxide seed and 80mL mixed solution are added in the reactor of polytetrafluoroethyllining lining, 60 DEG C
Lower reaction 6h, is washed with deionized 3 times after taking-up, and air drying 4h obtains silicon dioxide fibre Dynamic Membrane；
d）Silicon dioxide fibre Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 9sccm is passed through, is reacted at 300 DEG C
1h, is obtained with ultra-hydrophobicity silicon dioxide fibre Dynamic Membrane；
e）Silicon dioxide fibre Dynamic Membrane is placed in tube furnace, the oxygen that flow is 5sccm is passed through, is reacted at 400 DEG C
1h, obtains the silicon dioxide fibre Dynamic Membrane with super hydrophilicity.
Renovation process：To contaminated super hydrophilic and superhydrophobic silica fiber Dynamic Membrane after repeatedly water-oil separating
It is immersed in the dilute hydrochloric acid solution that 100mL concentration is 0.01mol/L, is taken out after 1h, deionized water is dried at washing 3 times, 60 DEG C
1h；Preparation process a~e is repeated, the selective Dynamic Membrane of wetting of regeneration is obtained.
Embodiment 3
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.001mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 70 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of copper mesh is immersed in 10s in 50mL zinc colloidal sols, 10min is dried at 60 DEG C, immersion 5 times is repeated,
Anneal 45min at 200 DEG C, obtains the copper mesh of coating zinc oxide seed；
c）It is 0. 1mol/L zinc acetates and the mixed solution that concentration is 0. 1mol/L ammonium fluorides to prepare 80mL concentration, will be coated
The copper mesh material of zinc oxide seed and 80mL mixed solution are added in the reactor of polytetrafluoroethyllining lining, are reacted at 60 DEG C
It is washed with deionized after 6h, taking-up 3 times, air drying 4h obtains copper mesh Dynamic Membrane；
d）Copper mesh Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 20sccm is passed through, reacts 1h at 400 DEG C, must have
There is ultra-hydrophobicity copper mesh Dynamic Membrane；
e）Copper mesh Dynamic Membrane is placed in tube furnace, the oxygen that flow is 25sccm is passed through, reacts 6h at 300 DEG C, must have
There is the copper mesh Dynamic Membrane of super hydrophilicity.
Renovation process：Contaminated super hydrophilic and super-hydrophobic copper mesh Dynamic Membrane after repeatedly water-oil separating is incited somebody to action to be immersed in
100mL concentration is in 0.01mol/L dilute hydrochloric acid solution, takes out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；Repeat
Preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiment 4
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.05mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 60 DEG C, obtains milky zinc colloidal sol；
b）10s, the drying 40min at 120 DEG C, repetition immersion in 50mL zinc colloidal sols by 10 square centimeters of nylon cloth film immersion
5 times, anneal 30min at 250 DEG C, obtains the nylon cloth of coating zinc oxide seed；
c）It is 0. 1mol/L zinc acetates and the mixed solution that concentration is 0.02mol/L ammoniacal liquor to prepare 80mL concentration, will coat oxygen
The mixed solution of the nylon cloth and 80mL of changing zinc seed is added in the reactor of polytetrafluoroethyllining lining, and 6h is reacted at 60 DEG C,
It is washed with deionized after taking-up 3 times, air drying 4h, obtains nylon cloth base Dynamic Membrane；
d）Nylon cloth base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 10sccm is passed through, 3h is reacted at 300 DEG C,
There must be ultra-hydrophobicity nylon cloth base Dynamic Membrane；
e）Nylon cloth base Dynamic Membrane is placed in tube furnace, the oxygen that flow is 15sccm is passed through, 3h is reacted at 300 DEG C,
There must be the nylon cloth base Dynamic Membrane of super hydrophilicity.
Renovation process：To contaminated super hydrophilic and super-hydrophobic nylon cloth base Dynamic Membrane immersion after repeatedly water-oil separating
In 100mL concentration in 0.01mol/L dilute hydrochloric acid solution, to be taken out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；Weight
Multiple preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiment 5
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.1mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring is to dissolving, and gained zinc acetate ethanol solution exists
Flow back 3h at 80 DEG C, obtains milky zinc colloidal sol.
b）By 10 square centimeters of two copper mesh film immersions in 50mL zinc colloidal sols 10s, at 60 DEG C dry 20min, repeat
Immersion 5 times, anneal 15min at 250 DEG C, obtains the copper mesh of coating zinc oxide seed；
c）It is 0.015mol/L zinc acetates and the mixed solution that concentration is 0.2mol/L ammonium chlorides to prepare 80mL concentration, will be coated
The copper mesh of zinc oxide seed and 80mL mixed solution are added in the reactor of polytetrafluoroethyllining lining, and 6h is reacted at 60 DEG C,
It is washed with deionized after taking-up 3 times, air drying 4h, obtains copper mesh base Dynamic Membrane；
d）Copper mesh base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 15sccm is passed through, reacts 3h at 300 DEG C, obtain
Dynamic Membrane is tieed up with ultra-hydrophobicity copper mesh base；
e）Copper mesh base Dynamic Membrane is placed in tube furnace, the oxygen that flow is 15sccm is passed through, reacts 6h at 350 DEG C, obtain
Copper mesh base Dynamic Membrane with super hydrophilicity.
Renovation process：Contaminated super hydrophilic and super-hydrophobic copper mesh base Dynamic Membrane after repeatedly water-oil separating is incited somebody to action to be immersed in
100mL concentration is in 0.01mol/L dilute hydrochloric acid solution, takes out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；Repeat
Preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiment 6
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.05 mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 60 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of cotton is immersed in 10s in 50mL zinc colloidal sols, 10min is dried at 80 DEG C, immersion 5 times is repeated,
Anneal 30min at 300 DEG C, obtains the cotton of coating zinc oxide seed；
c）It is 0.01mol/L zinc acetates and the mixed solution that concentration is 0.015mol/L urea to prepare 80mL concentration, will coat oxygen
The mixed solution of the cotton and 80mL of changing zinc seed is added in the reactor of polytetrafluoroethyllining lining, is reacted 6h at 80 DEG C, is taken
It is washed with deionized after going out 3 times, air drying 4h, obtains cotton base Dynamic Membrane；
d）Cotton base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 20sccm is passed through, reacts 3h at 400 DEG C, obtain
With ultra-hydrophobicity cotton base Dynamic Membrane；
e）Cotton base Dynamic Membrane is placed in tube furnace, the oxygen that flow is 25sccm is passed through, reacts 3h at 300 DEG C, obtain
Cotton base Dynamic Membrane with super hydrophilicity.
Renovation process：Contaminated super hydrophilic and super-hydrophobic cotton base Dynamic Membrane after repeatedly water-oil separating is incited somebody to action to be immersed in
100mL concentration is in 0.01mol/L dilute hydrochloric acid solution, takes out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；Repeat
Preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiment 7
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.01mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 70 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of silicon dioxide fibrous membrane is immersed in 10s in 50mL zinc colloidal sols, 40min, weight are dried at 60 DEG C
Soak 5 times again, anneal 15min at 350 DEG C, obtains the silicon dioxide fibrous membrane of coating zinc oxide seed；
c）It is 0.01mol/L zinc acetates and the mixed solution that concentration is 0. 1mol/L ammonium nitrate to prepare 80mL concentration, will be coated
The silicon dioxide fibrous membrane of zinc oxide seed and 80mL mixed solution are added in the reactor of polytetrafluoroethyllining lining, 60 DEG C
Lower reaction 6h, is washed with deionized 3 times after taking-up, and air drying 4h obtains silicon dioxide fibre Dynamic Membrane；
d）Silicon dioxide fibre Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 20sccm is passed through, is reacted at 200 DEG C
6h, is obtained with ultra-hydrophobicity silicon dioxide fibre Dynamic Membrane；
e）Silicon dioxide fibre Dynamic Membrane is placed in tube furnace, the oxygen that flow is 5sccm is passed through, is reacted at 300 DEG C
1h, obtains the silicon dioxide fibre Dynamic Membrane with super hydrophilicity.
Renovation process：To contaminated super hydrophilic and superhydrophobic silica fiber Dynamic Membrane after repeatedly water-oil separating
It is immersed in the dilute hydrochloric acid solution that 100mL concentration is 0.01mol/L, is taken out after 1h, deionized water is dried at washing 3 times, 60 DEG C
1h；Preparation process a~e is repeated, the selective Dynamic Membrane of wetting of regeneration is obtained.
Embodiment 8
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.001mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 70 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of copper mesh is immersed in 10s in 50mL zinc colloidal sols, 10min is dried at 100 DEG C, immersion 5 times is repeated,
Anneal 45min at 200 DEG C, obtains the copper mesh of coating zinc oxide seed；
c）The mixed solution that 80mL concentration is 0.1mol/L zinc acetates and concentration is 0.02mol/L hexamethylene tetramines is prepared,
The mixed solution of the copper mesh material of coating zinc oxide seed and 80mL is added in the reactor of polytetrafluoroethyllining lining, 60 DEG C
Lower reaction 6h, is washed with deionized 3 times, air drying 4h after taking-up, obtains copper mesh base Dynamic Membrane；
d）Copper mesh base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 9sccm is passed through, reacts 1h at 200 DEG C, must have
There is ultra-hydrophobicity copper mesh base Dynamic Membrane；
e）Copper mesh base Dynamic Membrane is placed in tube furnace, the oxygen that flow is 20sccm is passed through, reacts 6h at 300 DEG C, obtain
Copper mesh base Dynamic Membrane with super hydrophilicity.
Renovation process：Contaminated super hydrophilic and super-hydrophobic copper mesh base Dynamic Membrane after repeatedly water-oil separating is incited somebody to action to be immersed in
100mL concentration is in 0.01mol/L dilute hydrochloric acid solution, takes out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；Repeat
Preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiment 9
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.01mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 80 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of stainless (steel) wire is immersed in 10s in 50mL zinc colloidal sols, 10min is dried at 120 DEG C, repeats to soak
5 times, anneal 30min at 300 DEG C, obtains the stainless (steel) wire of coating zinc oxide seed；
c）Prepare the mixing that 80mL concentration is 0.015mol/L zinc acetates with concentration is 0.05mol/L hexamethylene tetramines molten
Liquid, the mixed solution of the stainless (steel) wire material of coating zinc oxide seed and 80mL is added to the reactor of polytetrafluoroethyllining lining
In, react and be washed with deionized after 6h, taking-up 3 times at 60 DEG C, air drying 4h obtains stainless steel base net Dynamic Membrane；
d）Stainless (steel) wire base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 10sccm is passed through, is reacted at 300 DEG C
3h, is obtained with ultra-hydrophobicity stainless (steel) wire base Dynamic Membrane；
e）Stainless (steel) wire Dynamic Membrane is placed in tube furnace, the oxygen that flow is 25sccm is passed through, 1h is reacted at 300 DEG C,
There must be the stainless (steel) wire base Dynamic Membrane of super hydrophilicity.
Renovation process：To contaminated super hydrophilic and super-hydrophobic stainless (steel) wire base Dynamic Membrane leaching after repeatedly water-oil separating
Steep in 100mL concentration in 0.01mol/L dilute hydrochloric acid solution, to be taken out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；
Preparation process a~e is repeated, the selective Dynamic Membrane of wetting of regeneration is obtained.
Embodiment 10
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.001mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 60 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of copper mesh is immersed in 10s in 50mL zinc colloidal sols, 20min is dried at 120 DEG C, immersion 5 times is repeated,
Anneal 15min at 350 DEG C, obtains the copper mesh of coating zinc oxide seed；
c）It is 0.01mol/L zinc acetates and the mixed solution that concentration is 0.2mol/L ammonium chlorides to prepare 80mL concentration, will coat oxygen
The mixed solution of the copper mesh material and 80mL of changing zinc seed is added in the reactor of polytetrafluoroethyllining lining, is reacted at 60 DEG C
It is washed with deionized after 5h, taking-up 3 times, air drying 4h, obtains copper mesh base Dynamic Membrane；
d）Copper mesh base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 15sccm is passed through, reacts 1h at 400 DEG C, obtain
With ultra-hydrophobicity copper mesh base Dynamic Membrane；
e）Copper mesh base Dynamic Membrane is placed in tube furnace, the oxygen that flow is 15sccm is passed through, reacts 6h at 300 DEG C, obtain
Copper mesh base Dynamic Membrane with super hydrophilicity.
Renovation process：Contaminated super hydrophilic and super-hydrophobic copper mesh base Dynamic Membrane after repeatedly water-oil separating is incited somebody to action to be immersed in
100mL concentration is in 0.01mol/L dilute hydrochloric acid solution, takes out after 1h, deionized water dries 3h at washing 3 times, 60 DEG C；Repeat
Preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiment 11
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.005mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring to dissolving, gained zinc acetate ethanol solution
Flow back 3h at 70 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of copper mesh is immersed in 10s in 50mL zinc colloidal sols, 10min is dried at 60 DEG C, immersion 5 times is repeated,
Anneal 30min at 250 DEG C, obtains the copper mesh of coating zinc oxide seed；
c）It is 0.05mol/L zinc acetates and the mixed solution that concentration is 0. 1mol/L ammonium nitrate to prepare 80mL concentration, will be coated
The copper mesh material of zinc oxide seed and 80mL mixed solution are added in the reactor of polytetrafluoroethyllining lining, are reacted at 60 DEG C
It is washed with deionized after 6h, taking-up 3 times, air drying 4h, obtains copper mesh base Dynamic Membrane；
d）Copper mesh base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 20sccm is passed through, reacts 6h at 200 DEG C, obtain
With ultra-hydrophobicity copper mesh base Dynamic Membrane；
e）Copper mesh base Dynamic Membrane is placed in tube furnace, the oxygen that flow is 10sccm is passed through, reacts 6h at 300 DEG C, obtain
Copper mesh base Dynamic Membrane with super hydrophilicity.
Renovation process：Contaminated super hydrophilic and super-hydrophobic copper mesh base Dynamic Membrane after repeatedly water-oil separating is incited somebody to action to be immersed in
100mL concentration is in 0.01mol/L dilute hydrochloric acid solution, takes out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；Repeat
Preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiment 12
A kind of preparation method of selective water-oil separating Dynamic Membrane, including：
a）0.1mol zinc acetates are added in 100mL absolute ethyl alcohols, strong stirring is to dissolving, and gained zinc acetate ethanol solution exists
Flow back 3h at 70 DEG C, obtains milky zinc colloidal sol；
b）10 square centimeters of nylon cloth is immersed in 10s in 50mL zinc colloidal sols, 10min is dried at 60 DEG C, immersion 5 is repeated
Secondary, anneal 45min at 200 DEG C, obtains the nylon cloth of coating zinc oxide seed；
c）Prepare the mixing that 80mL concentration is 0.01mol/L zinc acetates with concentration is 0.01mol/L hexamethylene tetramines molten
Liquid, the mixed solution of the nylon cloth material of coating zinc oxide seed and 80mL is added to the reactor of polytetrafluoroethyllining lining
In, react and be washed with deionized after 6h, taking-up 3 times at 60 DEG C, air drying 4h obtains nylon cloth base Dynamic Membrane；
d）Nylon cloth base Dynamic Membrane is placed in tube furnace, the hydrogen that flow is 90sccm is passed through, 3h is reacted at 300 DEG C,
There must be ultra-hydrophobicity nylon cloth base Dynamic Membrane；
e）Nylon cloth base Dynamic Membrane is placed in tube furnace, the oxygen that flow is 25sccm is passed through, 4h is reacted at 300 DEG C,
There must be the nylon cloth base Dynamic Membrane of super hydrophilicity.
Renovation process：To contaminated super hydrophilic and super-hydrophobic nylon cloth base Dynamic Membrane immersion after repeatedly water-oil separating
In 100mL concentration in 0.01mol/L dilute hydrochloric acid solution, to be taken out after 1h, deionized water dries 1h at washing 3 times, 60 DEG C；Weight
Multiple preparation process a~e, obtains the selective Dynamic Membrane of wetting of regeneration.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification is made, or other related technical fields are directly or indirectly used in,
Similarly it is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of selective water-oil separating Dynamic Membrane, it is characterised in that comprise the following steps：
a）Add 0.001 by every 100mL absolute ethyl alcohols~0.1mol zinc acetates based on, zinc acetate is added in absolute ethyl alcohol, strength
Stirring is to dissolving, and gained zinc acetate ethanol solution flows back 3h at 60~80 DEG C, obtains milky zinc colloidal sol；
b）Add 5 by basement membrane every square centimeter~10mL zinc colloidal sols based on, basement membrane is immersed in 10s in zinc colloidal sol, at 60~120 DEG C
Under, 10~40min is dried, immersion 3~9 times is repeated, anneal 15~45min at 200~350 DEG C, obtains coating zinc oxide seed
Perforated substrate film, wherein, the basement membrane be copper mesh, silicon dioxide fibrous membrane, stainless (steel) wire, cotton, nylon cloth in one kind
Or a variety of combinations；
c）By 0.01~0.1mol/L zinc acetate aqueous solutions, with 0.01~0.2mol/L pH adjusting agent aqueous solutions, isometric mixing
Uniformly, zinc acetate pH adjusting agent mixed solution is obtained；Based on every square centimeter plus 10mL zinc acetate pH adjusting agent mixed solutions, it will wrap
The perforated substrate film and zinc acetate pH adjusting agent solution for covering zinc oxide seed are added in polytetrafluoroethyllining lining reactor, 60~
6~16h is reacted at 120 DEG C, is washed with deionized after taking-up 2~5 times, 4~8h of air drying obtains many of zinc oxide precoated shet
Pore separation membrane, wherein the pH adjusting agent is in ammonium chloride, ammonium fluoride, ammonium nitrate, hexamethylene tetramine, ammoniacal liquor, urea etc.
One or more combinations；
d）It is passed through by every square centimeter based on 9~20sccm of flow hydrogen, the porous diffusion barrier of zinc oxide precoated shet is placed on
In tube furnace, 1~6h, preferably 3h are reacted at 200~400 DEG C, preferably 300 DEG C, the zinc oxide precoating with ultra-hydrophobicity is obtained
The porous separation Dynamic Membrane of layer；
e）By the oxymeter every square centimeter for being passed through 5~25sccm of flow, the porous diffusion barrier of zinc oxide precoated shet is placed on
In tube furnace, 1~6h, preferably 3h are reacted at 300~400 DEG C, preferably 300 DEG C, the zinc oxide precoating with super hydrophilicity is obtained
The porous separation Dynamic Membrane of layer.
2. the preparation method of selective water-oil separating Dynamic Membrane according to claim 1, it is characterised in that：By every in step a)
100mL absolute ethyl alcohols add 0.1mol zinc acetate meter, and zinc acetate is added in absolute ethyl alcohol, strong stirring to dissolving, gained
Zinc acetate ethanol solution flows back 3h at 60 DEG C, obtains milky zinc colloidal sol.
3. the preparation method of selective water-oil separating Dynamic Membrane according to claim 1, it is characterised in that：By base in step b)
Film immersion 10s in zinc colloidal sol, at 60 DEG C, dries 20min.
4. the preparation method of selective water-oil separating Dynamic Membrane according to claim 1, it is characterised in that：Described in step b)
Anneal 15min at 250 DEG C, obtains the perforated substrate film of coating zinc oxide seed.
5. the preparation method of selective water-oil separating Dynamic Membrane according to claim 1, it is characterised in that：Described in step b)
Basement membrane is silicon dioxide fibrous membrane.
6. the preparation method of selective water-oil separating Dynamic Membrane according to claim 1, it is characterised in that：Will in step c)
0.01mol/L zinc acetate aqueous solutions, it is isometric well mixed with 0.01mol/L pH adjusting agent aqueous solutions, obtain zinc acetate pH tune
Save agent mixed solution.
7. the preparation method of selective water-oil separating Dynamic Membrane according to claim 1, it is characterised in that：Described in step c)
PH adjusting agent is hexamethylene tetramine.
8. the selective water-oil separating Dynamic Membrane prepared according to any methods describeds of claim 1-7, it is characterised in that：Institute
Dynamic Membrane is stated to be formed in membrane surface growth in situ by the secondary filming with wetting selectivity.
9. selective water-oil separating Dynamic Membrane according to claim 8, it is characterised in that：The basement membrane is porous fibre net
Film, described filming is the zinc oxide with wetting selectivity, and its thickness is 200~2000nm.
10. the application of selective water-oil separating Dynamic Membrane described in a kind of claim 8 or 9, it is characterised in that：It is applied to oil
Water is separated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710346237.9A CN107081075B (en) | 2017-05-17 | 2017-05-17 | Preparation method and application of selective oil-water separation dynamic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710346237.9A CN107081075B (en) | 2017-05-17 | 2017-05-17 | Preparation method and application of selective oil-water separation dynamic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107081075A true CN107081075A (en) | 2017-08-22 |
| CN107081075B CN107081075B (en) | 2020-02-21 |
Family
ID=59608263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710346237.9A Expired - Fee Related CN107081075B (en) | 2017-05-17 | 2017-05-17 | Preparation method and application of selective oil-water separation dynamic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107081075B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191093A (en) * | 2017-12-29 | 2018-06-22 | 中国海洋石油集团有限公司 | A kind of air supporting-Dynamic Membrane integrated separation device and separation method suitable for condensed oil sewage processing |
| CN108246254A (en) * | 2018-01-16 | 2018-07-06 | 江苏大学 | A kind of preparation method and product of the adjustable biomass carbon tunica fibrosa of wetability |
| CN108570850A (en) * | 2018-02-15 | 2018-09-25 | 湖北大学 | A kind of preparation method of the excellent super wetting woven fabric of stabilization patience for water-oil separating |
| CN108611630A (en) * | 2018-04-11 | 2018-10-02 | 燕山大学 | A kind of hierarchical Z nO/Cu3(PO4)2Controllable immersing composite material and preparation method |
| CN108837707A (en) * | 2018-05-21 | 2018-11-20 | 江苏大学 | A kind of preparation method of the selective water-oil separationg film of wetting separated on demand |
| CN109011707A (en) * | 2018-08-28 | 2018-12-18 | 江苏大学 | A kind of water-oil separating material and preparation method thereof based on building castoff |
| CN111437730A (en) * | 2019-01-17 | 2020-07-24 | 南京林业大学 | Preparation method of hydrophobic super-oleophylic nanofiber membrane capable of adapting to severe environment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748596A (en) * | 2009-12-22 | 2010-06-23 | 天津理工大学 | Method for developing zinc oxide super-hydrophobic nano structure on textile fabric |
| CN103191855A (en) * | 2013-04-18 | 2013-07-10 | 天津大学 | Super-hydrophobic composite porous film and preparation method thereof |
| CN104261695A (en) * | 2014-09-19 | 2015-01-07 | 武汉工程大学 | Preparation method of transparent super-hydrophobic zinc oxide coating |
| CN104525951A (en) * | 2014-12-31 | 2015-04-22 | 华南理工大学 | Preparation method for super-hydrophobic/super-oleophilic oil-water separation copper fiber felt |
| CN104726834A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | Hydrophilic and hydrophobic-reversible switching titanium dioxide nanometer film material and preparation method thereof |
| WO2017050749A1 (en) * | 2015-09-24 | 2017-03-30 | Luxembourg Institute Of Science And Technology (List) | Biocompatible, porous filtering membranes including photocatalysts |
-
2017
- 2017-05-17 CN CN201710346237.9A patent/CN107081075B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748596A (en) * | 2009-12-22 | 2010-06-23 | 天津理工大学 | Method for developing zinc oxide super-hydrophobic nano structure on textile fabric |
| CN103191855A (en) * | 2013-04-18 | 2013-07-10 | 天津大学 | Super-hydrophobic composite porous film and preparation method thereof |
| CN104726834A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | Hydrophilic and hydrophobic-reversible switching titanium dioxide nanometer film material and preparation method thereof |
| CN104261695A (en) * | 2014-09-19 | 2015-01-07 | 武汉工程大学 | Preparation method of transparent super-hydrophobic zinc oxide coating |
| CN104525951A (en) * | 2014-12-31 | 2015-04-22 | 华南理工大学 | Preparation method for super-hydrophobic/super-oleophilic oil-water separation copper fiber felt |
| WO2017050749A1 (en) * | 2015-09-24 | 2017-03-30 | Luxembourg Institute Of Science And Technology (List) | Biocompatible, porous filtering membranes including photocatalysts |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191093A (en) * | 2017-12-29 | 2018-06-22 | 中国海洋石油集团有限公司 | A kind of air supporting-Dynamic Membrane integrated separation device and separation method suitable for condensed oil sewage processing |
| CN108246254A (en) * | 2018-01-16 | 2018-07-06 | 江苏大学 | A kind of preparation method and product of the adjustable biomass carbon tunica fibrosa of wetability |
| CN108246254B (en) * | 2018-01-16 | 2020-02-21 | 江苏大学 | Preparation method of biomass carbon fiber membrane with adjustable wettability and product |
| CN108570850A (en) * | 2018-02-15 | 2018-09-25 | 湖北大学 | A kind of preparation method of the excellent super wetting woven fabric of stabilization patience for water-oil separating |
| CN108570850B (en) * | 2018-02-15 | 2021-03-02 | 湖北大学 | Preparation method of super-wetting woven fabric with excellent stability and tolerance for oil-water separation |
| CN108611630A (en) * | 2018-04-11 | 2018-10-02 | 燕山大学 | A kind of hierarchical Z nO/Cu3(PO4)2Controllable immersing composite material and preparation method |
| CN108837707A (en) * | 2018-05-21 | 2018-11-20 | 江苏大学 | A kind of preparation method of the selective water-oil separationg film of wetting separated on demand |
| CN108837707B (en) * | 2018-05-21 | 2020-11-03 | 江苏大学 | Preparation method of wetting selective oil-water separation membrane capable of being separated according to needs |
| CN109011707A (en) * | 2018-08-28 | 2018-12-18 | 江苏大学 | A kind of water-oil separating material and preparation method thereof based on building castoff |
| CN109011707B (en) * | 2018-08-28 | 2020-09-25 | 江苏大学 | Oil-water separation material based on construction waste and preparation method thereof |
| CN111437730A (en) * | 2019-01-17 | 2020-07-24 | 南京林业大学 | Preparation method of hydrophobic super-oleophylic nanofiber membrane capable of adapting to severe environment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107081075B (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107081075A (en) | A kind of preparation method and applications of selective water-oil separating Dynamic Membrane | |
| CN103623709B (en) | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof | |
| CN109433013A (en) | A kind of graphene oxide and the composite modified membrane material and preparation method thereof of graphite phase carbon nitride | |
| CN108771982A (en) | A kind of preparation method of super-hydrophobic/super-oleophilic high efficiency oil-water seperation film | |
| Li et al. | The poly (vinyl alcohol-co-ethylene) nanofiber/silica coated composite membranes for oil/water and oil-in-water emulsion separation | |
| CN111001190B (en) | Preparation method and application of emulsion separation membrane with controllable wettability | |
| Yang et al. | A less harmful system of preparing robust fabrics for integrated self-cleaning, oil-water separation and water purification | |
| CN106283851A (en) | A kind of graphene oxide modification oil-water separation filter paper and preparation method thereof | |
| CN105126647B (en) | A kind of high efficiency oil-water separates the preparation method of composite hyperfiltration membrane | |
| CN106637929A (en) | Hydrophobic and oleophilic cotton fiber and preparation method and application thereof | |
| CN108479118A (en) | A kind of water-oil separating steel wire of graphene oxide/poly-dopamine surface modification | |
| Sun et al. | Multi-scaled, hierarchical nanofibrous membrane for oil/water separation and photocatalysis: Preparation, characterization and properties evaluation | |
| CN111604032A (en) | Janus nitrogen-doped carbon nanofiber film and preparation method and application thereof | |
| CN107008161B (en) | A kind of modified composite membrane of Prussian blue/carboxy methylcellulose gel and preparation method and purposes | |
| CN106283894A (en) | A kind of graphene oxide modification filter paper and preparation method and application | |
| Yuan et al. | Robust and switchable superwetting sponge-like membrane: Towards on-demand emulsion separation and aqueous pollutant degradation | |
| Zhang et al. | Polyester fabrics coated with cupric hydroxide and cellulose for the treatment of kitchen oily wastewater | |
| CN112755805A (en) | Underwater super-oleophobic two-dimensional nanoscale mica sheet oil-water separation membrane and preparation method and application thereof | |
| CN108246254A (en) | A kind of preparation method and product of the adjustable biomass carbon tunica fibrosa of wetability | |
| CN109621740B (en) | Pore-diameter-controllable super-hydrophobic polymeric membrane and preparation method thereof | |
| CN115745050A (en) | Photo-thermal evaporation and photocatalysis synergistic sewage treatment material and preparation method thereof | |
| CN113005775B (en) | Preparation method of porous super-hydrophobic carbon fiber membrane suitable for severe environment | |
| CN109316778A (en) | A kind of method that immersion coating polymer nano granules prepare super-hydrophobic copper mesh | |
| CN110292866B (en) | Preparation method and application of super-hydrophilic oleophobic oil-water separation membrane | |
| Wang et al. | Simple preparation of UV-absorbing and magnetic superhydrophobic membranes by one-step electrospinning for effective oil–water separation |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200221 Termination date: 20200517 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |