CN105854630A - Forward-osmosis film and preparation method thereof - Google Patents
Forward-osmosis film and preparation method thereof Download PDFInfo
- Publication number
- CN105854630A CN105854630A CN201610311533.0A CN201610311533A CN105854630A CN 105854630 A CN105854630 A CN 105854630A CN 201610311533 A CN201610311533 A CN 201610311533A CN 105854630 A CN105854630 A CN 105854630A
- Authority
- CN
- China
- Prior art keywords
- solution
- graphene oxide
- membrane
- forward osmosis
- polyamide
- 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
- B01D71/021—Carbon
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D67/0083—Thermal after-treatment
-
- 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
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a forward-osmosis film and a preparation method thereof. The forward-osmosis film comprises a support layer, the support layer is a superfilter film, oxidized graphene, and 0-2nd generation polyamide-amide blend. The forward-osmosis film is high in water flux, graphene layers are not easy to shed among layers and from the superfilter film as interlayer distance among oxidized graphene layers is constant, and distance among the oxidized graphene layers can be adjusted. Meanwhile, the forward-osmosis film has high cutoff performance for negative and positive ions in the solution, and the overall cutoff performance of the film is optimized.
Description
Technical field
The invention belongs to technical field of membrane separation, be specifically related to a kind of forward osmosis membrane and system thereof
Preparation Method.
Background technology
Broadly, the permoselective membrane of all dense non-porous can serve as just oozing
Antireflective film material uses, and such as, research worker in early days carries out during positive penetration study used
Forward osmosis membrane has animal's bladder, rubber, nitrocellulose, pottery, reverse osmosis membrane and nanofiltration
Film etc..Carrying out along with positive penetration study, it has been found that when passing through film with these selectivitys
When carrying out positive permeability test, obtained membrane flux is well below theoretical value.Forward osmosis membrane
With the difference of traditional pressure drive membrane be it to requirement of mechanical strength the highest without
Bear impressed pressure；The stratum disjunctum of forward osmosis membrane relative good to be possessed and support
The main cause of Rotating fields is that long-term contacting with solution is wanted in its both sides.Preferably just permeate
Film has following feature: (1) active layer to ensure enough compactness, it is thus possible to
There is higher salt-stopping rate；(2) active layer to possess preferable hydrophilic, such that it is able to
Ensure higher membrane flux, fouling membrane can also be reduced simultaneously；(3) for concentration difference in reducing
Polarization, is preferably selected thin and that porosity is big supporting layer；(4) in order to extend the life-span of film,
The film with higher mechanical strength should be selected；(5) being can be in large-scale pH value limit
And various differently composed solution works, film should have certain acid and alkali resistance, salt
Ability Deng corrosion.
By HTI company of the U.S. (Hydration Technology Incorporation) by turning mutually
Active layer prepared by change method and the Triafol T (CTA) of porous support layer structure
Forward osmosis membrane is the forward osmosis membrane of currently the only commercialization.It is to use hydrophilic energy
Enough provide the polyester screen of mechanical support as backing material, in waste water reclamation, sea
Multiple fields such as water desalination have and use widely.But this product still suffers from the most serious
Interior concentration polarization phenomenon, causes the permeable pressure head of film both sides to decline to a great extent, makes under water flux
Fall.Interior concentration polarization has become the obstacle hindering the development of forward osmosis membrane isolation technics.
Summary of the invention
In view of this, the invention provides a kind of forward osmosis membrane, described forward osmosis membrane includes
Supporting layer；Described supporting layer is the copolymer of ultrafilter membrane, graphene oxide, polyamide-amide.
Alternatively, described forward osmosis membrane also includes cortex；Described cortex is multiple on supporting layer
The aramid layer closed.
Alternatively, described ultrafilter membrane is gathered by the one in polysulfones, polyether sulfone or polyacrylonitrile
Laminate material is made.
Alternatively, the aperture of described ultrafilter membrane is 0.01 μm～0.05 μm.
Present invention also offers the preparation method of forward osmosis membrane, comprise the following steps:
(1) ultrafilter membrane is immersed in positively charged solution, and it is shaken,
Make inside ultrafilter membrane with positive charge；
(2) by graphene oxide ultrasonic disperse in water, obtaining graphene oxide concentration is
The graphene oxide water solution of 0.1g/L～10g/L；
(3) by polyamide-amide solution that concentration is 1～5mg/L and the oxygen in step (2)
Functionalized graphene aqueous solution, wherein, polyamide-amide solution and graphene oxide water solution
Volume ratio be 1:1～1:5, prepare mixed liquor；
(4) mixed liquor in step (3) is filled into ultrafilter membrane table through ultrafilter membrane vacuum
Face, the ultrafilter membrane after filtration is standby；
(5) ultrafilter membrane in step (4) is placed in baking oven after heat treatment, is just preparing
Permeable membrane.
Alternatively, step (6) is also included: put by the forward osmosis membrane prepared in step (5)
In oil-phase solution；The solute of described oil-phase solution is the small-molecule substance containing acyl chlorides.
Alternatively, the solvent of described oil-phase solution is normal hexane or Isopars.
Alternatively, the described small-molecule substance containing acyl chlorides be m-phthaloyl chloride, to benzene two
One or more in formyl chloride, pyromellitic trimethylsilyl chloride, equal benzene four formyl chloride.
Alternatively, by polyamide-amide solution and the oxidation in step (2) in step (3)
Graphene aqueous solution mixes, and adds additive afterwards；Described additive is ethanol solution, third
Alcoholic solution, pyridine solution, the one in phenol solution.
Alternatively, by polyamide-amide solution and the oxidation in step (2) in step (3)
Graphene aqueous solution mixes, wherein polyamide-amide solution and the body of graphene oxide water solution
Long-pending ratio is 1:1～1:3；In described graphene oxide water solution, the concentration of graphene oxide is
0.1g/L～10g/L.
The forward osmosis membrane of the present invention compared with prior art, has the advantage that
Compared to existing technology, the forward osmosis membrane of the present invention, by graphene oxide vacuum filtration
To the surface of ultrafilter membrane, owing to surface of graphene oxide and edge contain substantial amounts of hydrophilic group
Group, effectively raises the hydrophilicity of ultrafilter membrane.Furthermore, by using aperture bigger
Ultrafilter membrane as supporting layer, thus reduce internal concentration polarization, be conducive to just improving
The flux of permeable membrane.
Meanwhile, surface and the edge of graphene oxide contains the oxygen-containing group can reacted in a large number
Group, such as epoxy, hydroxyl and carboxyl functional group etc., has the strongest hydrophilic, therefore
If graphene oxide cross-links between layers, then when graphene oxide contacts with water
Will necessarily occur swelling, not only between layers can be peeling-off inside graphene oxide,
Even partial oxidation of graphite alkene layer can unclamp from ultrafiltration supporting layer, split away off.Therefore,
The present invention intends using and had both been provided that multiple primary amine group, also has a large amount of secondary amine and uncle simultaneously
The monomer of amine structure, i.e. polyamide-amide dendrimer are blended with graphene oxide, utilize oxygen
Condensation is there is or opens in carboxyl or epoxide group that functionalized graphene surface and edge contain with amido
Ring reacts, to realize the fixing of graphene oxide interlayer.
Further, prepare for core with ethylenediamine due to this polyamide-amide dendrimer.
For 0 PAMAM, there are 4 primary amine groups on its surface, for 1 generation polyamide-
Amine, its surface then has 8 primary amine groups, 2 PAMAMs, and its surface has 16
Individual primary amine group.Owing to the primary amine group number on polyamide-amide surface is along with the growth of algebraically
In exponential increase, and polyamide-amide molecular volume the most constantly increases, and therefore uses different generation
The polyamide-amide of number is as cross-linking agent, it is possible to adjust graphene oxide interlamellar spacing.Need reason
Solving, polyamide-amide dendrimer is internal containing substantial amounts of primary, secondary amine groups, its point
With positive charge in minor structure, and substantial amounts of negative charge is contained on the surface of graphene oxide.
Therefore, both forward osmosis membranes of preparation above-mentioned anions and canons in saline solution is had
Repulsive interaction, thus improve its interception capacity.It is understood that polyamide-amide molecule
Algebraically the highest, with positive changes the most.
Further, the copolymer of ultrafilter membrane, graphene oxide, polyamide-amide is formed
Supporting layer be placed in the oil-phase solution of the small-molecule substance containing acyl chlorides, now graphite oxide
The residue amido having neither part nor lot in cross-linking reaction in the carboxyl on alkene surface and polyamide-amide molecule will
With acid chloride groups generation interface polymerization reaction, generate ultra-thin polyamide cortex.This activity
Cortex is for maintaining the interlamellar spacing of graphene oxide, it is achieved the effectively catching to solute, rises
Arrive important function.
In sum, the present invention provide forward osmosis membrane, have above-mentioned many advantages and
Practical value, and there are no in like product similar design publish or use and
Really belong to innovation, create preferable practical function.
Detailed description of the invention
The claim of the present invention is done further by the mode below in conjunction with specific embodiment
Describing in detail, but be not intended that any limitation of the invention, anyone weighs in the present invention
The amendment of the limited number of time made in profit claimed range, still in scope of the presently claimed invention
Within.
The invention provides a kind of forward osmosis membrane, described forward osmosis membrane includes supporting layer；Institute
Stating supporting layer is ultrafilter membrane, graphene oxide, 0～2 copolymers of polyamide-amide in generation.
Above-mentioned, after adding graphene oxide, owing to graphene oxide is a kind of hydrophilic
Nano-particle, when graphene oxide is filled on ultrafilter membrane by vacuum, due to oxidation
Graphene contains substantial amounts of hydrophilic functional group, and its specific surface area is the biggest simultaneously, and this is non-
Often being conducive to the flowing of hydrone, the membrane flux thus resulting in forward osmosis membrane dramatically increases,
Hydrophilicity improves.
Meanwhile, surface and the edge of graphene oxide contains the oxygen-containing group can reacted in a large number
Group, such as hydroxyl, carboxyl and epoxy-functional etc., has the strongest hydrophilic, therefore
If graphene oxide cross-links between layers, then when graphene oxide contacts with water
Will necessarily occur swelling, not only between layers can be peeling-off inside graphene oxide,
Even partial oxidation of graphite alkene layer can unclamp from ultrafiltration supporting layer, split away off.Therefore,
The present invention intends using and had both been provided that multiple primary amine group, also has a large amount of secondary amine and uncle simultaneously
The monomer of amine structure, i.e. polyamide-amide dendrimer are blended with graphene oxide, so that
The graphene oxide obtaining lamellar forms firm interlayer crosslinking.
It is to be appreciated that this polyamide-amide dendrimer is to be prepared into ethylenediamine for core
Arrive.For 0 PAMAM, there are 4 primary amine groups on its surface, gathers for 1 generation
Amide-amine, its surface then has 8 primary amine groups, 2 PAMAMs, and its surface has
There are 16 primary amine groups.Owing to the primary amine group number on polyamide-amide surface is along with algebraically
Increase in exponential increase, and polyamide-amide molecular volume the most constantly increases, and therefore uses not
With the polyamide-amide of algebraically as cross-linking agent, provide for adjusting graphene oxide interlamellar spacing
May.
Further, described forward osmosis membrane also includes cortex；Described cortex is on supporting layer
Compound aramid layer.
The support stratification that the copolymer of ultrafilter membrane, graphene oxide, polyamide-amide is formed
In the oil-phase solution of the small-molecule substance containing acyl chlorides, the now carboxylic of surface of graphene oxide
The residue amido having neither part nor lot in cross-linking reaction in base and polyamide-amide molecule will be with acid chloride groups
There is interface polymerization reaction, generate ultra-thin polyamide cortex.This activity cortex is for dimension
Hold the interlamellar spacing of graphene oxide, it is achieved the effectively catching to solute, serve important work
With.
Material blended membrane material blending and modifying is 2 kinds or polymer of more than two kinds to be passed through
The method of physical mixed prepares blend film, to improve the combination property of film.
Further, described ultrafilter membrane is by the one in polysulfones, polyether sulfone or polyacrylonitrile
Polymeric material is made.
Above-mentioned, containing sulfuryl on this molecular backbone, cause this base polymer to have good
Heat stability, chemical stability, acid-alkali-corrosive-resisting performance, excellent mechanical performance and
Prominent creep-resistant property.But weatherability and UV resistant are slightly worse, belong to hydrophobic film material
Material.
Although polyether sulfone has lot of advantages, but its membrane material hydrophilic is poor, easily causes
Protein and natural organic matter are in film surface adsorption.This is to cause polyether sulfone filtering fouling membrane
Main cause.Additionally, the resistance tocrocking that the surface topography of film, charging performance etc. are to film
Can also have an impact.Therefore should add above-mentioned graphene oxide, polyamide-amide prepares blend film
Material, in addition modified.
Polyacrylonitrile is to be obtained through Raolical polymerizable by monomers acrylonitrile.Macromole
Acrylonitrile unit in chain connects head-tail mode and is connected.It is mainly used in polyacrylonitrile processed fine
Dimension.The advantage of polyacrylonitrile fibre be weatherability and sun-resistant property good, in outdoor placement 18
The 77% of original intensity can also be kept after individual month.Also there is chemical-resistant reagent, the most inorganic
Acid, bleaching powder, hydrogen peroxide and the characteristic of general organic reagent.
Further, the aperture of described ultrafilter membrane is 0.01 μm～0.05 μm.
Above-mentioned, the separation of ultrafilter membrane depends on the size of membrane aperture, fine and close support
Film can bring serious internal concentration polarization problem, for concentration polarization in reducing, preferably selects
Select thin and that porosity is big supporting layer.
Present invention also offers the preparation method of a kind of forward osmosis membrane, comprise the following steps:
(1) ultrafilter membrane is immersed in positively charged solution, and it is shaken,
Make inside ultrafilter membrane with positive charge；
Above-mentioned, ultrafilter membrane total charge is regulated.It is understood that this band
The solution of positive charge can be polyetherimide solution, it is also possible to is PAH hydrochloric acid
Saline solution, dodecyl dimethyl ammonium chloride solution, dimethyl diallyl ammonium chloride are molten
One in liquid.
(2) by graphene oxide ultrasonic disperse in water, obtaining graphene oxide concentration is
The graphene oxide water solution of 0.1g/L～10g/L；
Above-mentioned, graphene oxide thin slice is Graphene product after chemical oxidation and stripping,
Graphene oxide is single atomic layer, can expand to tens of at any time on lateral dimension
Micron, therefore, its construct trans general chemistry and the typical size of material science.Oxygen
Functionalized graphene can be considered the flexible material of a kind of non-traditional kenel, have polymer, colloid,
Thin film, and amphiphilic characteristic.Graphene oxide is considered hydrophilic for a long time
Material, because it has superior dispersibility in water, but, related experiment result shows
Showing, graphene oxide is of virtually amphipathic.
(3) by polyamide-amide solution that concentration is 1～5mg/L and the oxygen in step (2)
Functionalized graphene aqueous solution, wherein, polyamide-amide solution and graphene oxide water solution
Volume ratio be 1:1～1:5, prepare mixed liquor；
Above-mentioned, polyamide-amide solution and graphene oxide water solution are prepared blend.Need
Should be understood that the polyamide-amide molecule in polyamide-amide solution can be different algebraically
Polyamide-amide, this polyamide-amide dendrimer prepares with ethylenediamine for core.Right
In 0 PAMAM, there are 4 primary amine groups on its surface, for 1.0 PAMAMs,
Its surface then has 8 primary amine groups.Primary amine group number due to polyamide-amide surface
Along with the growth of algebraically is in exponential increase, and polyamide-amide molecular volume the most constantly increases,
Therefore the polyamide-amide of the different algebraically of employing is as cross-linking agent, for adjusting graphene oxide layer
Spacing provides possibility.
(4) mixed liquor in step (3) is filled into ultrafilter membrane table through ultrafilter membrane vacuum
Face, the ultrafilter membrane after filtration is standby；
Above-mentioned, use the method for sucking filtration that blends described above is laid on the table of ultrafilter membrane uniformly
Face.
Vacuum when preferably vacuum filters is 20kPa to 80kPa.
(5) ultrafilter membrane in step (4) is placed in baking oven after heat treatment, is just preparing
Permeable membrane.
Above-mentioned, blends described above is fixed on uniformly the surface of ultrafilter membrane.
Preferably, the ultrafilter membrane after filtration is placed in baking oven, and oven temperature is 60～150 DEG C.
Preferably, the time being placed in baking oven is 1～3h.
Preferably, the forward osmosis membrane lucifuge after baking oven heat treatment deposits 12～48h.
Further, step (6) is also included: the forward osmosis membrane that will prepare in step (5)
It is placed in oil-phase solution；The solute of described oil-phase solution is the small-molecule substance containing acyl chlorides.
Above-mentioned, for alleviating internal concentration polarization, first introduce at ultrafiltration membrane surface and have two
The graphene oxide of dimension layer structure, and by the method that vacuum filters, make graphite oxide
Alkene is laid in ultrafiltration membrane surface stratiform, by many amine monomers i.e. polyamide-amide to oxygen
It is fixing that functionalized graphene interlayer carries out crosslinking, finally by above-mentioned film and the little molecule thing containing acyl chlorides
Matter contacts with the active cortex preparing ultrafilter membrane.Therefore, graphene oxide layer on support membrane
Introducing so that be no longer open state with the aperture above the support membrane that active layer contacts,
Therefore, from the design of membrane structure, can suitably relax the aperture of supporting layer and carry out hole
Footpath optimizes, and is conducive to alleviating internal concentration polarization, and improves permeation flux.
From discussed above, the highly-hydrophilic performance of graphene oxide so that it is have non-
Often it is prone to occur interlayer to depart from the trend even departing from ultrafiltration membranes, therefore on ultrafilter membrane
After side introduces graphene oxide, in addition it is also necessary to by the parent having neither part nor lot in reaction in graphene oxide
Water base group protects, and prevents it the most swelling.Therefore by above-mentioned load graphite oxide
The support membrane of alkene oil phase with the small-molecule substance containing acyl chlorides further contacts, now oxygen
The carboxyl on functionalized graphene surface and polyamide-amide molecule have neither part nor lot in the residue of cross-linking reaction
Amido will generate ultra-thin polyamide activity skin with acid chloride groups generation interface polymerization reaction
Layer.
This activity cortex is for maintaining the interlamellar spacing of graphene oxide, it is achieved have solute
Effect retains, and serves important function.
Preferably, the time being placed in oil phase is 30～180s.
Then being placed in baking oven by above-mentioned prepared forward osmosis membrane, oven temperature is 20 DEG C and arrives
100 DEG C, the time is 0～40min.
Further, the solvent of described oil-phase solution is normal hexane or Isopars.
Above-mentioned, normal hexane or Isopars all can preferably dissolve little point containing acyl chlorides
Sub-material.
Further, the described small-molecule substance containing acyl chlorides be m-phthaloyl chloride, to benzene
One or more in dimethyl chloride, pyromellitic trimethylsilyl chloride, equal benzene four formyl chloride.
Above-mentioned, all can prepare above-mentioned ultra-thin polyamide activity cortex.
Further, by polyamide-amide solution and the oxygen in step (2) in step (3)
Functionalized graphene aqueous solution, adds additive afterwards；Described additive is ethanol solution,
Propanol solution, pyridine solution, the one in phenol solution.
Above-mentioned, ethanol solution, propanol solution, pyridine solution, phenol solution can be catalyzed
Polyamide-amide and the reaction of graphene oxide.
Further, by polyamide-amide solution and the oxygen in step (2) in step (3)
Functionalized graphene aqueous solution, wherein polyamide-amide solution and graphene oxide water solution
Volume ratio is 1:1～1:3；In described graphene oxide water solution, the concentration of graphene oxide is
0.1g/L～10g/L.
Above-mentioned, polyamide-amide solution when aoxidizes stone with the volume of graphene oxide water solution
In ink aqueous solution, the performance preparing forward osmosis membrane is all had relatively by the concentration of graphene oxide
Big impact.
Embodiment 1
(1) polysulphones hyperfiltration membrane that aperture is 0.01 μm is immersed in polyetherimide solution
In, and it is shaken, make inside polysulphones hyperfiltration membrane with positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 0.1g/L
Graphene oxide water solution；
(3) by polyamide-amide solution that concentration is 1mg/L and the oxidation in step (2)
Graphene aqueous solution mixes, wherein polyamide-amide solution and the body of graphene oxide water solution
Long-pending ratio is 1:1, prepares mixed liquor；
(4) mixed liquor in step (3) is filtered through polysulphones hyperfiltration membrane vacuum, vacuum
During filtration, pressure is 0.4bar, and the polysulphones hyperfiltration membrane after filtration is standby；
(5) polysulphones hyperfiltration membrane in step (4) is placed in baking oven after heat treatment, heat
During process, temperature is 60 DEG C, and the time of heat treatment is 3h, prepares forward osmosis membrane.
Embodiment 2
(1) poly (ether-sulfone) ultrafiltration membrane that aperture is 0.02 μm is immersed in dimethyl two allyl
In ammonium chloride, and it is shaken, make inside poly (ether-sulfone) ultrafiltration membrane with positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 1g/L
Graphene oxide water solution；
(3) by polyamide-amide solution that concentration is 5mg/L and the oxidation in step (2)
Graphene aqueous solution mixes, wherein polyamide-amide solution and the body of graphene oxide water solution
Long-pending ratio is 1:2, and addition ethanol solution, as catalyst, prepares mixed liquor；
(4) mixed liquor in step (3) is filtered through poly (ether-sulfone) ultrafiltration membrane vacuum, very
During empty filtration, pressure is 0.6bar, and the poly (ether-sulfone) ultrafiltration membrane after filtration is standby；
(5) poly (ether-sulfone) ultrafiltration membrane in step (4) is placed in baking oven after heat treatment,
During heat treatment, temperature is 80 DEG C, and the time of heat treatment is 2.5h, prepares forward osmosis membrane.
(6) forward osmosis membrane prepared in step (5) is placed in oil-phase solution 30 seconds；
The solute of described oil-phase solution is the small-molecule substance containing acyl chlorides, wherein, oil-phase solution
Solvent is normal hexane solvent, and solute is m-phthaloyl chloride.
Embodiment 3
(1) polyacrylonitrile ultrafiltration film that aperture is 0.03 μm is immersed in dimethyl diene
In propyl ammonium chloride solution, and it is shaken, make the internal band of polyacrylonitrile ultrafiltration film
There is positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 5g/L
Graphene oxide water solution；
(3) by polyamide-amide solution that concentration is 3mg/L and the oxidation in step (2)
Graphene aqueous solution mixes, wherein polyamide-amide solution and the body of graphene oxide water solution
Long-pending ratio is 1:3, and addition propanol solution, as catalyst, prepares mixed liquor；
(4) mixed liquor in step (3) is filtered through polyacrylonitrile ultrafiltration film vacuum,
When vacuum filters, pressure is 0.8bar, and the polyacrylonitrile ultrafiltration film after filtration is standby；
(5) polyacrylonitrile ultrafiltration film in step (4) is placed in baking oven after heat treatment,
During heat treatment, temperature is 100 DEG C, and the time of heat treatment is 2h, prepares forward osmosis membrane.
(6) forward osmosis membrane prepared in step (5) is placed in oil-phase solution 90 seconds；
The solute of described oil-phase solution is the small-molecule substance containing acyl chlorides, wherein, oil-phase solution
Solvent is Isopars, and solute is paraphthaloyl chloride.
Embodiment 4
(1) polyacrylonitrile ultrafiltration film that aperture is 0.05 μm is immersed in PAH
In HCI solution, and it is shaken, make inside polyacrylonitrile ultrafiltration film with just
Electric charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 10g/L
Graphene oxide water solution；
(3) by polyamide-amide solution that concentration is 4mg/L and the oxidation in step (2)
Graphene aqueous solution mixes, wherein polyamide-amide solution and the body of graphene oxide water solution
Long-pending ratio is 1:4, and addition pyridine solution, as catalyst, prepares mixed liquor；
(4) mixed liquor in step (3) is filtered through polyacrylonitrile ultrafiltration film vacuum,
When vacuum filters, pressure is 0.4bar, and the polyacrylonitrile ultrafiltration film after filtration is standby；
(5) polyacrylonitrile ultrafiltration film in step (4) is placed in baking oven after heat treatment,
During heat treatment, temperature is 130 DEG C, and the time of heat treatment is 1.5h, prepares forward osmosis membrane.
(6) forward osmosis membrane prepared in step (5) is placed in oil-phase solution 120 seconds
Clock；The solute of described oil-phase solution is the small-molecule substance containing acyl chlorides, and wherein, oil phase is molten
The solvent of liquid is normal hexane solvent, and solute is pyromellitic trimethylsilyl chloride.
Embodiment 5
(1) polyacrylonitrile ultrafiltration film that aperture is 0.02 μm is immersed in dodecyl two
In ammonio methacrylate Solutions Solution, and it is shaken, in making polyacrylonitrile ultrafiltration film
Portion is with positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 8g/L
Graphene oxide water solution；
(3) by polyamide-amide solution that concentration is 2mg/L and the oxidation in step (2)
Graphene aqueous solution mixes, wherein polyamide-amide solution and the body of graphene oxide water solution
Long-pending ratio is 1:5, and addition phenol solution, as catalyst, prepares mixed liquor；
(4) mixed liquor in step (3) is filtered through polyacrylonitrile ultrafiltration film vacuum,
When vacuum filters, pressure is 0.8bar, and the polyacrylonitrile ultrafiltration film after filtration is standby；
(5) polyacrylonitrile ultrafiltration film in step (4) is placed in baking oven after heat treatment,
During heat treatment, temperature is 150 DEG C, and the time of heat treatment is 0.5h, prepares forward osmosis membrane.
(6) forward osmosis membrane prepared in step (5) is placed in oil-phase solution 180 seconds
Clock；The solute of described oil-phase solution is the small-molecule substance containing acyl chlorides, and wherein, oil phase is molten
The solvent of liquid is Isopars, and solute is equal benzene four formyl chloride.
Matched group 1
The commercialization thin layer composite forward osmosis membrane of HTI company.
For further illustrating the technique effect of the present invention, to embodiment 1～5 and matched group 1
In the positive permeance property of forward osmosis membrane test, with 0.25M citric acid three sodium solution
As drawing liquid, deionized water is as material liquid.In inventor's existing test instrunment condition
Under, test result is shown in Table 1.
Table 1 forward osmosis membrane the performance test results
| Embodiment | Water flux (L/m2h) | Solute flux (mol/m2h) |
| Embodiment 1 | 35 | 0.020 |
| Embodiment 2 | 27 | 0.025 |
| Embodiment 3 | 30 | 0.010 |
| Embodiment 4 | 28 | 0.020 |
| Embodiment 5 | 35 | 0.015 |
| Matched group 1 | 10 | 0.150 |
Claims (10)
1. a forward osmosis membrane, it is characterised in that: described forward osmosis membrane includes supporting layer；
Described supporting layer is ultrafilter membrane, graphene oxide, 0～2 blends of polyamide-amide in generation.
2. forward osmosis membrane as claimed in claim 1, it is characterised in that: described just permeate
Film also includes cortex；Described cortex is aramid layer compound on supporting layer.
3. forward osmosis membrane as claimed in claim 1, it is characterised in that: described ultrafilter membrane
It is made up of a kind of polymeric material in polysulfones, polyether sulfone or polyacrylonitrile.
4. forward osmosis membrane as claimed in claim 1, it is characterised in that: described ultrafilter membrane
Aperture be 0.01 μm～0.05 μm.
5. a preparation method for forward osmosis membrane as claimed in claim 1, its feature exists
In: comprise the following steps:
(1) ultrafilter membrane is immersed in positively charged solution, and it is shaken,
Make inside ultrafilter membrane with positive charge；
(2) by graphene oxide ultrasonic disperse in water, obtaining graphene oxide concentration is
The graphene oxide water solution of 0.1g/L～10g/L；
(3) by polyamide-amide solution that concentration is 1～5mg/L and the oxygen in step (2)
Functionalized graphene aqueous solution, wherein, polyamide-amide solution and graphene oxide water solution
Volume ratio be 1:1～1:5, prepare mixed liquor；
(4) mixed liquor in step (3) is filled into ultrafilter membrane table through ultrafilter membrane vacuum
Face, the ultrafilter membrane after filtration is standby；
(5) ultrafilter membrane in step (4) is placed in baking oven after heat treatment, is just preparing
Permeable membrane.
6. the preparation method of forward osmosis membrane as claimed in claim 5, it is characterised in that:
Also include step (6): be placed in oil-phase solution by the forward osmosis membrane prepared in step (5)；
The solute of described oil-phase solution is the small-molecule substance containing acyl chlorides.
7. the preparation method of forward osmosis membrane as claimed in claim 6, it is characterised in that:
The solvent of described oil-phase solution is normal hexane or Isopars.
8. the preparation method of forward osmosis membrane as claimed in claim 6, it is characterised in that:
The described small-molecule substance containing acyl chlorides is m-phthaloyl chloride, paraphthaloyl chloride, equal benzene
One or more in three formyl chlorides, equal benzene four formyl chloride.
9. the preparation method of forward osmosis membrane as claimed in claim 5, it is characterised in that:
By polyamide-amide solution and the graphene oxide water solution in step (2) in step (3)
Mixing, adds additive afterwards；Described additive is ethanol solution, propanol solution, pyridine
Solution, the one in phenol solution.
10. the preparation method of forward osmosis membrane as claimed in claim 5, it is characterised in that:
By polyamide-amide solution and the graphene oxide water solution in step (2) in step (3)
Mixing, wherein polyamide-amide solution with the volume ratio of graphene oxide water solution is
1:1～1:3；In described graphene oxide water solution, the concentration of graphene oxide is 1g/L
～10g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610311533.0A CN105854630B (en) | 2016-05-11 | 2016-05-11 | A kind of forward osmosis membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610311533.0A CN105854630B (en) | 2016-05-11 | 2016-05-11 | A kind of forward osmosis membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105854630A true CN105854630A (en) | 2016-08-17 |
| CN105854630B CN105854630B (en) | 2019-03-29 |
Family
ID=56631814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610311533.0A Active CN105854630B (en) | 2016-05-11 | 2016-05-11 | A kind of forward osmosis membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105854630B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106964263A (en) * | 2017-04-27 | 2017-07-21 | 山东金城石墨烯科技有限公司 | A kind of preparation method and application of the graphene NF membrane of solvent resistant resistant |
| CN107188569A (en) * | 2017-06-18 | 2017-09-22 | 长沙无道工业设计有限公司 | A kind of desalinization composite membrane based on graphene oxide and preparation method thereof |
| CN107261859A (en) * | 2017-06-22 | 2017-10-20 | 浙江工业大学 | Preparation method of graphene oxide/polymer solvent-resistant composite nanofiltration membrane |
| CN108043242A (en) * | 2017-11-30 | 2018-05-18 | 商丘师范学院 | A kind of preparation method of the adjustable graphene oxide membrane of surface wettability energy |
| CN108786464A (en) * | 2018-06-15 | 2018-11-13 | 武汉工程大学 | The preparation method for graphene oxide NF membrane that flux is adjustable |
| CN108786499A (en) * | 2018-06-15 | 2018-11-13 | 武汉工程大学 | The preparation method of the controllable carboxylated graphene oxide NF membrane of flux |
| CN109999662A (en) * | 2019-03-26 | 2019-07-12 | 黑龙江八一农垦大学 | A kind of amphoteric ion nanofiltration membrane and preparation method thereof |
| WO2019165840A1 (en) * | 2018-02-27 | 2019-09-06 | 深圳大学 | Forward osmosis membrane, and preparation method therefor |
| CN110575757A (en) * | 2019-09-29 | 2019-12-17 | 哈工程先进技术研究院(招远)有限公司 | preparation method of nanofiltration membrane for reducing sewage chromaticity |
| CN111036094A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Chlorine-resistant composite reverse osmosis membrane, and preparation method and application thereof |
| CN111437736A (en) * | 2020-04-09 | 2020-07-24 | 浙江美易膜科技有限公司 | Organic composite membrane containing graphene oxide and preparation method thereof |
| CN115025622A (en) * | 2022-07-13 | 2022-09-09 | 浙江工业大学 | High-flux reverse osmosis membrane based on multi-dimensional graphene oxide modification and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301758A (en) * | 2013-05-20 | 2013-09-18 | 哈尔滨工业大学 | Preparation method of graphene/polypyrrole composited forward osmosis membrane |
| CN103338845A (en) * | 2011-06-20 | 2013-10-02 | Lg化学株式会社 | Reverse osmosis membrane having superior salt rejection and permeate flow, and method for manufacturing same |
| CN104474919A (en) * | 2014-12-15 | 2015-04-01 | 济南大学 | High-performance flat-type cellulose acetate/graphene blend forward osmosis membrane |
-
2016
- 2016-05-11 CN CN201610311533.0A patent/CN105854630B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103338845A (en) * | 2011-06-20 | 2013-10-02 | Lg化学株式会社 | Reverse osmosis membrane having superior salt rejection and permeate flow, and method for manufacturing same |
| CN103301758A (en) * | 2013-05-20 | 2013-09-18 | 哈尔滨工业大学 | Preparation method of graphene/polypyrrole composited forward osmosis membrane |
| CN104474919A (en) * | 2014-12-15 | 2015-04-01 | 济南大学 | High-performance flat-type cellulose acetate/graphene blend forward osmosis membrane |
Non-Patent Citations (1)
| Title |
|---|
| 金丽梅等: "基于树状分子聚酰胺-胺（PAMAM）的复合纳滤膜制备及性能研究", 《高校化学工程学报》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106964263A (en) * | 2017-04-27 | 2017-07-21 | 山东金城石墨烯科技有限公司 | A kind of preparation method and application of the graphene NF membrane of solvent resistant resistant |
| CN107188569A (en) * | 2017-06-18 | 2017-09-22 | 长沙无道工业设计有限公司 | A kind of desalinization composite membrane based on graphene oxide and preparation method thereof |
| CN107261859A (en) * | 2017-06-22 | 2017-10-20 | 浙江工业大学 | Preparation method of graphene oxide/polymer solvent-resistant composite nanofiltration membrane |
| CN107261859B (en) * | 2017-06-22 | 2020-01-14 | 浙江工业大学 | Preparation method of graphene oxide/polymer solvent-resistant composite nanofiltration membrane |
| CN108043242A (en) * | 2017-11-30 | 2018-05-18 | 商丘师范学院 | A kind of preparation method of the adjustable graphene oxide membrane of surface wettability energy |
| CN108043242B (en) * | 2017-11-30 | 2021-03-16 | 商丘师范学院 | Preparation method of graphene oxide film with adjustable surface wettability |
| WO2019165840A1 (en) * | 2018-02-27 | 2019-09-06 | 深圳大学 | Forward osmosis membrane, and preparation method therefor |
| CN108786464A (en) * | 2018-06-15 | 2018-11-13 | 武汉工程大学 | The preparation method for graphene oxide NF membrane that flux is adjustable |
| CN108786499A (en) * | 2018-06-15 | 2018-11-13 | 武汉工程大学 | The preparation method of the controllable carboxylated graphene oxide NF membrane of flux |
| CN108786464B (en) * | 2018-06-15 | 2021-06-01 | 武汉工程大学 | Preparation method of flux-adjustable graphene oxide nanofiltration membrane |
| CN111036094A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Chlorine-resistant composite reverse osmosis membrane, and preparation method and application thereof |
| CN111036094B (en) * | 2018-10-15 | 2022-07-12 | 中国石油化工股份有限公司 | Chlorine-resistant composite reverse osmosis membrane, and preparation method and application thereof |
| CN109999662A (en) * | 2019-03-26 | 2019-07-12 | 黑龙江八一农垦大学 | A kind of amphoteric ion nanofiltration membrane and preparation method thereof |
| CN110575757A (en) * | 2019-09-29 | 2019-12-17 | 哈工程先进技术研究院(招远)有限公司 | preparation method of nanofiltration membrane for reducing sewage chromaticity |
| CN110575757B (en) * | 2019-09-29 | 2021-12-10 | 哈工程先进技术研究院(招远)有限公司 | Preparation method of nanofiltration membrane for reducing sewage chromaticity |
| CN111437736A (en) * | 2020-04-09 | 2020-07-24 | 浙江美易膜科技有限公司 | Organic composite membrane containing graphene oxide and preparation method thereof |
| CN115025622A (en) * | 2022-07-13 | 2022-09-09 | 浙江工业大学 | High-flux reverse osmosis membrane based on multi-dimensional graphene oxide modification and preparation method thereof |
| CN115025622B (en) * | 2022-07-13 | 2023-03-28 | 浙江工业大学 | High-flux reverse osmosis membrane based on multi-dimensional graphene oxide modification and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105854630B (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105854630A (en) | Forward-osmosis film and preparation method thereof | |
| Kheirieh et al. | Application and modification of polysulfone membranes | |
| Yang et al. | Dopamine: just the right medicine for membranes | |
| US11433358B2 (en) | Composite reverse osmosis membrane and preparation method thereof | |
| Hong et al. | Potential ion exchange membranes and system performance in reverse electrodialysis for power generation: A review | |
| CN106861449B (en) | A kind of quaternary ammoniated graphene oxide composite nano filter membrane and preparation method thereof | |
| CN105642129A (en) | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof | |
| US10143974B2 (en) | Forward osmosis-based separation membrane based on multilayer thin film, using crosslinking between organic monomers, and preparation method therefor | |
| Zunita et al. | Graphene oxide-inorganic composite membrane: a review | |
| CN112275140A (en) | Polyamide nanofiltration membrane with patterned surface and preparation method thereof | |
| Ghanbari et al. | Approaches of membrane modification for water treatment | |
| Fang et al. | Evaluating the antifouling properties of poly (ether sulfone)/sulfonated poly (ether sulfone) blend membranes in a full-size membrane module | |
| CN115105973B (en) | Nanofiltration membrane preparation method for efficient magnesium-lithium separation and application | |
| Xu et al. | Synthetic polymer materials for forward osmosis (FO) membranes and FO applications: a review | |
| CN113398777A (en) | Three-layer structure composite forward osmosis membrane with MXene drainage layer and preparation method thereof | |
| CN113019146A (en) | Preparation method of ultrahigh-flux composite nanofiltration membrane | |
| CN112058094A (en) | Loose nanofiltration membrane and preparation method thereof | |
| CN111389238A (en) | Composite nanofiltration membrane based on modified polyolefin microporous substrate and preparation method thereof | |
| CN112619438B (en) | Methanol-resistant polyamide reverse osmosis membrane and preparation method thereof | |
| CN109999662A (en) | A kind of amphoteric ion nanofiltration membrane and preparation method thereof | |
| CN109647222A (en) | Method for preparing high-flux high-rejection-rate aromatic polyamide composite reverse osmosis membrane by using tannic acid modified base membrane | |
| CN115055061B (en) | Preparation method of polyamide composite nanofiltration membrane with high permeability selectivity | |
| CN105664739A (en) | Preparation method of highly hydrophilic polysulfone ultrafiltration membrane | |
| Tong et al. | Fabricating novel PVDF-g-IBMA copolymer hydrophilic ultrafiltration membrane for treating papermaking wastewater with good antifouling property | |
| CN113509848B (en) | Method for preparing polyether block amide pervaporation composite membrane based on liquid-liquid interface |
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 |