CN108380047A - Graphene oxide composite nano filter membrane and preparation method thereof with ion selectivity separation - Google Patents
Graphene oxide composite nano filter membrane and preparation method thereof with ion selectivity separation Download PDFInfo
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- CN108380047A CN108380047A CN201810101565.7A CN201810101565A CN108380047A CN 108380047 A CN108380047 A CN 108380047A CN 201810101565 A CN201810101565 A CN 201810101565A CN 108380047 A CN108380047 A CN 108380047A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000000926 separation method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010410 layer Substances 0.000 claims abstract description 82
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- 239000011229 interlayer Substances 0.000 claims abstract description 47
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 29
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 241000446313 Lamella Species 0.000 claims abstract description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 33
- 150000002500 ions Chemical class 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 24
- 239000008346 aqueous phase Substances 0.000 claims description 21
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- 239000004909 Moisturizer Substances 0.000 claims description 10
- 230000002745 absorbent Effects 0.000 claims description 10
- 239000002250 absorbent Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 230000001333 moisturizer Effects 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 239000002352 surface water Substances 0.000 claims description 7
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000005501 phase interface Effects 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000010148 water-pollination Effects 0.000 abstract description 7
- 238000001728 nano-filtration Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 3
- 238000012876 topography Methods 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 description 9
- 238000010926 purge Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D71/56—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of graphene oxide composite nano filter membranes and preparation method thereof with ion selectivity separation.Graphene oxide composite nano filter membrane is composite membrane, nanoscale separating layer including non-woven fabrics supporting layer, Polymer interlayers and functionalization, the nanoscale separating layer of non-woven fabrics supporting layer, Polymer interlayers and functionalization is set gradually from top to bottom, includes monolithic layer nano graphene oxide in the nanoscale separating layer of functionalization.Non-woven fabrics supporting layer is functionalization non-woven fabrics, using integral multi-layered structure.Polymer interlayers material is polysulfones, and section pore structure is asymmetric spongy and finger-like pore mixed structure.The present invention in interfacial polymerization process by introducing monolithic layer nano graphene oxide, improve the hydrophily and ion transportation of nanofiltration film surface, again since the pattern of monolithic layer nano graphene oxide is lamella pleated structure, the surface topography for imparting NF membrane pleated structure improves the surface area of NF membrane.
Description
Technical field
The present invention relates to Nanofiltration-membrane technique field more particularly to a kind of graphene oxide with ion selectivity separation are multiple
Close NF membrane and preparation method thereof.
Background technology
NF membrane be between ultrafiltration and it is reverse osmosis between novel membrane separation technique, prepare high retention, high-throughput and anti-pollution
Type NF membrane is always research hotspot, however how to realize that the balance of flux and rejection between the two is always a problem.
In recent years, GO (graphene oxide, graphene oxide) is due to its special structure and performance always research
Hot spot.GO is a kind of derivative of graphene, is substantially the same with graphene-structured, the two dimension only constituted in one layer of carbon atom
It is connected with a large amount of oxygen-containing hydrophilic functional groups, such as-OH ,-O- ,-COOH on the basal plane that space infinitely extends ,-C=O etc., thus
There is good dispersibility in water.GO films have liquid water ultrafast transmission rate, and in terms of ion isolation, GO has ion
Select the characteristic penetrated.
Currently, there are no realize the method for being effectively bonded together GO and NF membrane in the prior art.
Invention content
The embodiment provides it is a kind of with ion selectivity separation graphene oxide composite nano filter membrane and its
Preparation method, to improve the hydrophily and ion transportation of nanofiltration film surface.
To achieve the goals above, this invention takes following technical solutions.
According to an aspect of the invention, there is provided a kind of graphene oxide composite nanometer filter with ion selectivity separation
Film, the graphene oxide composite nano filter membrane be composite membrane, including non-woven fabrics supporting layer, Polymer interlayers and functionalization are received
The nanoscale separating layer of meter level separating layer, the non-woven fabrics supporting layer, Polymer interlayers and functionalization is set successively from top to bottom
It sets, includes monolithic layer nano graphene oxide in the nanoscale separating layer of the functionalization.
Further, the pattern of the monolithic layer nano graphene oxide is lamella pleated structure.
Further, the non-woven fabrics supporting layer is functionalization non-woven fabrics, and using integral multi-layered structure, thickness is in 95 μ
M, unit area grammes per square metre are 76g/m2, air permeability 2cc/cm2/sec。
Further, the Polymer interlayers material is polysulfones, and layer thickness is 30 μm of ± 2um, section pore structure right and wrong
The spongy and finger-like pore mixed structure of symmetric form, pore diameter range is between 0.001 μm to 10 μm；
Further, the nanoscale separating layer of the functionalization is the PA membrane of piperazine system, the water of the PA membrane
Phase monomer includes piperazine, additive, acid absorbent, moisturizer, and the oil phase monomer of the PA membrane is pyromellitic trimethylsilyl chloride, this is poly-
The solvent of amide film is IsoparG, IsoparE, n-hexane, ethyl cyclohexane, normal heptane are one such or several.
Further, the piperazine concentration is between 0.3-1%；
The additive be monolithic layer nano graphene oxide, lamellar spacing 0.5-5nm, a diameter of ＜ 400nm of lamella,
Content is 10ppm-500ppm；
The acid absorbent is organic amine, content 0.5-3%；
The moisturizer be small molecule alcohol, content 0.5-4%,
The pH value of the aqueous phase monomers is 8-12,
A concentration of 0.05%-1% of the oil phase monomer pyromellitic trimethylsilyl chloride.
According to another aspect of the present invention, a kind of graphene oxide with ion selectivity separation is provided compound to receive
The preparation method of filter membrane, including；
(1) prepared by Polymer interlayers：Non-woven fabrics supporting layer diaphragm is chosen, polymer feed liquid is homogeneously applied to described
The surface of non-woven fabrics supporting layer diaphragm, by adjusting the distance between coating head and non-woven fabrics supporting layer diaphragm and polymer feed liquid
Inlet amount adjust the thickness of non-woven fabrics supporting layer, passing through gel slot, rinse bath, quenching tank later makes non-woven fabrics support tunic
Piece cleans and sizing, obtains the counterdie of Polymer interlayers；
(2) prepared by the nanoscale separating layer of functionalization：Water phase containing graphene oxide is ultrasonically treated, water phase is made
Solution uniformly mixes, and the single-side impregnated aqueous phase solution 5S-20min of the counterdie of the Polymer interlayers is gone by air knife purging
It is thin that one layer of aqueous solution is formed except the surface water phase of the counterdie of the Polymer interlayers, on the counterdie of the Polymer interlayers
Film, then 5s-1min will be kept in organic phase solution of the counterdie dipping containing pyromellitic trimethylsilyl chloride of Polymer interlayers, pass through baking
Case makes water phase that interface polymerization reaction setting time occur with oil phase, and it is compound to obtain the graphene oxide that there is ion selectivity to detach
NF membrane.
Further, the counterdie of the Polymer interlayers of preparation is soaked in deionized water and is stayed with spare.
Further, the temperature of the baking oven is 60-110 DEG C, and optimum temperature is 80 DEG C, and the setting time is 1-
5min。
The present invention is by interfacial polymerization process it can be seen from the technical solution that embodiments of the invention described above provide
Monolithic layer nano graphene oxide is introduced, improves the hydrophily and ion transportation of nanofiltration film surface, and due to monolithic layer
The pattern of nano graphene oxide is lamella pleated structure, imparts the surface topography of NF membrane pleated structure, improves nanofiltration
The surface area of film makes graphene oxide composite nano filter membrane have higher water flux, and shows to divalent Ca2+、Mg2+Ion
With higher removal rate, to monovalent Na+、K+The performance of the relatively low removal rate of ion.
The additional aspect of the present invention and advantage will be set forth in part in the description, these will become from the following description
Obviously, or practice through the invention is recognized.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without creative efforts, others are can also be obtained according to these attached drawings
Attached drawing.
Fig. 1 is a kind of surface Electronic Speculum schematic diagram of polysulfones middle layer provided in an embodiment of the present invention；
Fig. 2 is a kind of surface Electronic Speculum schematic diagram of NF membrane provided in an embodiment of the present invention；
Fig. 3 is a kind of surface Electronic Speculum schematic diagram of graphene oxide composite nano filter membrane provided in an embodiment of the present invention；
Fig. 4 is a kind of PIP＆PIP-GO contact angles schematic diagram provided in an embodiment of the present invention.
PIP-GO is significantly improved compared with PIP hydrophilies
Specific implementation mode
Embodiments of the present invention are described below in detail, the example of the embodiment is shown in the accompanying drawings, wherein from beginning
Same or similar element or element with the same or similar functions are indicated to same or similar label eventually.Below by ginseng
The embodiment for examining attached drawing description is exemplary, and is only used for explaining the present invention, and is not construed as limiting the claims.
Those skilled in the art of the present technique are appreciated that unless expressly stated, singulative " one " used herein, " one
It is a ", " described " and "the" may also comprise plural form.It is to be further understood that is used in the specification of the present invention arranges
It refers to there are the feature, integer, step, operation, element and/or component, but it is not excluded that presence or addition to take leave " comprising "
Other one or more features, integer, step, operation, element, component and/or their group.It should be understood that when we claim member
Part is " connected " or when " coupled " to another element, it can be directly connected or coupled to other elements, or there may also be
Intermediary element.In addition, " connection " used herein or " coupling " may include being wirelessly connected or coupling.Wording used herein
"and/or" includes any cell of one or more associated list items and all combines.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein (including technology art
Language and scientific terminology) there is meaning identical with the general understanding of the those of ordinary skill in fields of the present invention.Should also
Understand, those terms such as defined in the general dictionary, which should be understood that, to be had and the meaning in the context of the prior art
The consistent meaning of justice, and unless defined as here, will not be with idealizing or the meaning of too formal be explained.
For ease of the understanding to the embodiment of the present invention, done further by taking several specific embodiments as an example below in conjunction with attached drawing
Explanation, and each embodiment does not constitute the restriction to the embodiment of the present invention.
An embodiment of the present invention provides a kind of graphene oxide composite nano filter membrane with ion selectivity separation, the oxidations
Graphene composite nanometer filtering film is composite membrane, includes the nanoscale separating layer of non-woven fabrics supporting layer, Polymer interlayers and functionalization,
The nanoscale separating layer of the non-woven fabrics supporting layer, Polymer interlayers and functionalization is set gradually from top to bottom.Functionalization
It include monolithic layer nano graphene oxide in nanoscale separating layer.
Non-woven fabrics supporting layer is functionalization non-woven fabrics, and using integral multi-layered structure, thickness is at 95 μm, unit area grammes per square metre
For 76g/m2, air permeability 2cc/cm2/sec。
Polymer interlayers material is polysulfones, and layer thickness is 30 μm of ± 2um, and section pore structure is asymmetric spongy
And finger-like pore mixed structure, pore diameter range is between 0.001 μm to 10 μm；
The nanoscale separating layer of functionalization is the PA membrane of piperazine system, and PA membrane aqueous phase monomers include piperazine, add
Add agent, acid absorbent, moisturizer, the oil phase monomer of the PA membrane is pyromellitic trimethylsilyl chloride, and the solvent of the PA membrane is
IsoparG, IsoparE, n-hexane, ethyl cyclohexane, normal heptane are one such or several.Piperazine concentration be 0.3-1% it
Between, preferably 0.5-0.75%.Additive is monolithic layer nano graphene oxide, lamellar spacing 0.5-5nm, a diameter of ＜ of lamella
400nm, content 10ppm-500ppm, preferably 50-200ppm.Acid absorbent is organic amine, content 0.5-3%.Moisturizer
For small molecule alcohol, content 0.5-4%.Aqueous phase monomers pH is 8~12, preferably pH=10-11.5.The equal benzene front three of oil phase monomer
Acyl chlorides a concentration of 0.05%-1%, preferably 0.08-0.5%.
The embodiment of the present invention additionally provides a kind of system of the graphene oxide composite nano filter membrane with ion selectivity separation
Preparation Method comprises the steps of：
(1) prepared by Polymer interlayers：The integrality of polymer middle support layer is to forming intact separating layer to closing weight
It wants, the present invention chooses non-woven fabrics supporting layer diaphragm, polymer feed liquid is equably applied in such a way that slit extrusion quantitatively coats
It is overlying on the surface of the non-woven fabrics supporting layer diaphragm, by adjusting the distance between coating head and non-woven fabrics supporting layer diaphragm and gathering
The inlet amount of material liquid is closed to adjust the thickness of non-woven fabrics supporting layer, passing through gel slot, rinse bath, quenching tank later makes non-woven fabrics
Supporting layer diaphragm cleans and sizing, obtains the counterdie of Polymer interlayers.Then, the counterdie of the Polymer interlayers of preparation is soaked
It steeps and is stayed in deionized water with spare, be sure not the counterdie of Polymer interlayers being positioned in dry air, prevent counterdie from losing
Water is ineffective.
(2) prepared by the nanoscale separating layer of functionalization：The water phase containing graphene oxide is ultrasonically treated first, is made
Aqueous phase solution uniformly mixes.Then, by the single-side impregnated aqueous phase solution 5S-20min of the counterdie of the Polymer interlayers, pass through wind
Knife purging removes the surface water phase of the counterdie of the Polymer interlayers, and one layer of water is formed on the counterdie of the Polymer interlayers
Solution film, it is sure not to be driven away water phase with rubber roller, the structure of destructible graphene oxide.Again by the counterdie of Polymer interlayers
Dipping keeps 5s-1min in the organic phase solution containing pyromellitic trimethylsilyl chloride, makes water phase that interface occur with oil phase by baking oven and gathers
Reaction setting time is closed, the graphene oxide composite nano filter membrane that there is ion selectivity to detach is obtained.It in practical applications, can be with
The baking oven that temperature in use is 60-110 DEG C, optimum temperature are 80 DEG C, continue interface polymerization reaction under this temperature condition
1-5min, optimum reacting time 2min.
Embodiment 1：
It is prepared by Polymer interlayers：
In such a way that slit extrusion quantitatively coats, polymer feed liquid is homogeneously applied to support layer surface, passes through tune
Section coating head at a distance from support interlayer and inlet amount adjusts support layer thickness, later by gel slot, rinse bath, quenching tank
So that diaphragm is cleaned and is shaped to get to Polymer interlayers, then the counterdie of preparation is soaked in deionized water and is stayed with spare.
It is prepared by the nanoscale separating layer of functionalization：
First by 0.6%PIP, 2.5% acid absorbent and 1.5% moisturizer, the aqueous phase solution of pH=11 carries out at ultrasound
30min is managed, it is made to be sufficiently mixed uniformly；
Oil phase monomer is 0.15% pyromellitic trimethylsilyl chloride, solvent IsoparE.
By the single-side impregnated aqueous phase solution 10S of counterdie, surface water phase is removed by the purging of air knife, then counterdie dipping is contained
10s is kept in the organic phase solution of pyromellitic trimethylsilyl chloride, makes aqueous phase monomers that interface polymerization reaction occur with oil phase monomer, finally leads to
2min is dried under the oven conditions that excess temperature is 80 DEG C, removes solvent.
Embodiment 2：
It is prepared by Polymer interlayers：
In such a way that slit extrusion quantitatively coats, polymer feed liquid is homogeneously applied to support layer surface, passes through tune
Section coating head at a distance from support interlayer and inlet amount adjusts support layer thickness, later by gel slot, rinse bath, quenching tank
So that diaphragm is cleaned and is shaped to get to Polymer interlayers, then the counterdie of preparation is soaked in deionized water and is stayed with spare.
It is prepared by the nanoscale separating layer of functionalization：
First by 0.6%PIP, 100ppm graphene oxide, 2.5% acid absorbent and 1.5% moisturizer, the water of pH=11
Phase solution carries out supersound process 30min, it is made to be sufficiently mixed uniformly；
Oil phase monomer is 0.15% pyromellitic trimethylsilyl chloride, solvent IsoparE.
By the single-side impregnated aqueous phase solution 10S of counterdie, surface water phase is removed by the purging of air knife, then counterdie dipping is contained
5s is kept in the organic phase solution of pyromellitic trimethylsilyl chloride, makes aqueous phase monomers that interface polymerization reaction occur with oil phase monomer, finally leads to
2min is dried under the oven conditions that excess temperature is 80 DEG C, removes solvent.
Embodiment 3：
It is prepared by Polymer interlayers：
In such a way that slit extrusion quantitatively coats, polymer feed liquid is homogeneously applied to support layer surface, passes through tune
Section coating head at a distance from support interlayer and inlet amount adjusts support layer thickness, later by gel slot, rinse bath, quenching tank
So that diaphragm is cleaned and is shaped to get to Polymer interlayers, then the counterdie of preparation is soaked in deionized water and is stayed with spare.
It is prepared by the nanoscale separating layer of functionalization：
First by 0.75%PIP, 2.5% acid absorbent and 1.5% moisturizer, the aqueous phase solution of pH=10.5 carries out ultrasound
30min is handled, it is made to be sufficiently mixed uniformly；
Oil phase monomer is 0.08% pyromellitic trimethylsilyl chloride, and solvent is n-hexane.
By the single-side impregnated aqueous phase solution 10S of counterdie, surface water phase is removed by the purging of air knife, then counterdie dipping is contained
5s is kept in the organic phase solution of pyromellitic trimethylsilyl chloride, makes aqueous phase monomers that interface polymerization reaction occur with oil phase monomer, finally leads to
Drying and shaping 2min under the oven conditions that excess temperature is 80 DEG C.
Embodiment 4：
It is prepared by Polymer interlayers：
In such a way that slit extrusion quantitatively coats, polymer feed liquid is homogeneously applied to support layer surface, passes through tune
Section coating head at a distance from support interlayer and inlet amount adjusts support layer thickness, later by gel slot, rinse bath, quenching tank
So that diaphragm is cleaned and is shaped to get to Polymer interlayers, then the counterdie of preparation is soaked in deionized water and is stayed with spare.
It is prepared by the nanoscale separating layer of functionalization：
First by 0.75%PIP, 200ppm graphene oxide, 2.5% acid absorbent and 1.5% moisturizer, pH=10.5
Aqueous phase solution carry out supersound process 30min, so that it is sufficiently mixed uniformly；
Oil phase monomer is 0.08% pyromellitic trimethylsilyl chloride, and solvent is n-hexane.
By the single-side impregnated aqueous phase solution 10S of counterdie, surface water phase is removed by the purging of air knife, then counterdie dipping is contained
5s is kept in the organic phase solution of pyromellitic trimethylsilyl chloride, makes aqueous phase monomers that interface polymerization reaction occur with oil phase monomer, finally leads to
Drying and shaping 2min under the oven conditions that excess temperature is 80 DEG C.
The graphene oxide composite nano filter membrane performance data such as following table with ion selectivity separation of the embodiment of the present invention
1, shown in table 2.
Table 1
| Performance | Example 1 | Example 2 | Example 3 | Example 4 |
| F/LMH | 60.47 | 71.80 | 53.46 | 62.31 |
| R/% | 97.63 | 97.42 | 98.06 | 97.88 |
Test condition：2000ppm MgSO4, 70psi, pH=7-8
Table 2
Test condition：250ppm CaCl260psi 7~8；
250ppm NaCl 60psi 7~8
Fig. 1 is a kind of surface Electronic Speculum schematic diagram of polysulfones middle layer provided in an embodiment of the present invention；Polysulfones interlayer surfaces
Pattern is porous structure.
Fig. 2 is a kind of surface Electronic Speculum schematic diagram of NF membrane provided in an embodiment of the present invention；Nanofiltration environmental microbes are smooth
It is smooth.
Fig. 3 is a kind of surface Electronic Speculum schematic diagram of graphene oxide composite nano filter membrane provided in an embodiment of the present invention；Oxidation
Graphene composite nanometer filter environmental microbes are lamella pleated structure.
Fig. 4 is a kind of PIP＆PIP-GO contact angles schematic diagram provided in an embodiment of the present invention, and PIP-GO composite membranes are compared with PIP films
Contact angle is remarkably decreased, and hydrophily significantly improves.
In conclusion the present invention is improved and is received by introducing monolithic layer nano graphene oxide in interfacial polymerization process
The hydrophily and ion transportation of filter membrane surface, and since the pattern of monolithic layer nano graphene oxide is lamella fold knot
Structure imparts the surface topography of NF membrane pleated structure, improves the surface area of NF membrane, makes graphene oxide composite nano filter membrane
With higher water flux, and show to divalent Ca2+、Mg2+Ion has higher removal rate, to monovalent Na+、K+Ion is relatively low
The performance of removal rate.
Graphene oxide composite nano filter membrane provided in an embodiment of the present invention with ion selectivity separation can be relatively low
Pressure under Ca in selective removal hard water2+、Mg2+Ion retains Na beneficial in water+、K+Ion, selective removal is certainly
Water harmful substance retains the small organic molecule and low price inorganic salts beneficial to body, and water outlet is in good taste, and container is not after heating up water
Incrustation scale is generated, drinking water and water purification field are can be widely applied to.In addition, since the introducing of graphene oxide improves NF membrane table
The hydrophily in face makes it show good antifouling property.Such graphene oxide with ion selectivity separation is compound
NF membrane has broad application prospects in fields such as drinking water, water purification and sewage disposal technologies.
One of ordinary skill in the art will appreciate that：Attached drawing is the schematic diagram of one embodiment, module in attached drawing or
Flow is not necessarily implemented necessary to the present invention.
Each embodiment in this specification is described in a progressive manner, identical similar portion between each embodiment
Point just to refer each other, and each embodiment focuses on the differences from other embodiments.Especially for device or
For system embodiment, since it is substantially similar to the method embodiment, so describing fairly simple, related place is referring to method
The part of embodiment illustrates.Apparatus and system embodiment described above is only schematical, wherein the conduct
The unit that separating component illustrates may or may not be physically separated, the component shown as unit can be or
Person may not be physical unit, you can be located at a place, or may be distributed over multiple network units.It can root
According to actual need that some or all of module therein is selected to achieve the purpose of the solution of this embodiment.Ordinary skill
Personnel are without creative efforts, you can to understand and implement.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
Subject to.
Claims (9)
1. a kind of graphene oxide composite nano filter membrane with ion selectivity separation, which is characterized in that the graphene oxide
Composite nanometer filtering film is composite membrane, includes the nanoscale separating layer of non-woven fabrics supporting layer, Polymer interlayers and functionalization, the nothing
The nanoscale separating layer of woven fabric supporting layer, Polymer interlayers and functionalization is set gradually from top to bottom, and the functionalization is received
It include monolithic layer nano graphene oxide in meter level separating layer.
2. the graphene oxide composite nano filter membrane according to claim 1 with ion selectivity separation, which is characterized in that
The pattern of the monolithic layer nano graphene oxide is lamella pleated structure.
3. the graphene oxide composite nano filter membrane according to claim 1 with ion selectivity separation, which is characterized in that
The non-woven fabrics supporting layer is functionalization non-woven fabrics, and using integral multi-layered structure, thickness is in 95 μm, unit area grammes per square metre
76g/m2, air permeability 2cc/cm2/sec。
4. the graphene oxide composite nano filter membrane according to claim 1 with ion selectivity separation, which is characterized in that
The Polymer interlayers material is polysulfones, and layer thickness is 30 μm of ± 2um, and section pore structure is asymmetric spongy and refers to
Shape hole mixed structure, pore diameter range is between 0.001 μm to 10 μm.
5. the graphene oxide composite nano filter membrane according to any one of claims 1 to 4 with ion selectivity separation,
It is characterized in that, the nanoscale separating layer of the functionalization is the PA membrane of piperazine system, the aqueous phase monomers packet of the PA membrane
Piperazine, additive, acid absorbent, moisturizer are included, the oil phase monomer of the PA membrane is pyromellitic trimethylsilyl chloride, the PA membrane
Solvent is IsoparG, IsoparE, n-hexane, ethyl cyclohexane, normal heptane are one such or several.
6. the graphene oxide composite nano filter membrane according to claim 5 with ion selectivity separation, it is characterised in that：
The piperazine concentration is between 0.3-1%；
The additive is monolithic layer nano graphene oxide, lamellar spacing 0.5-5nm, a diameter of ＜ 400nm of lamella, content
For 10ppm-500ppm；
The acid absorbent is organic amine, content 0.5-3%；
The moisturizer be small molecule alcohol, content 0.5-4%,
The pH value of the aqueous phase monomers is 8-12,
A concentration of 0.05%-1% of the oil phase monomer pyromellitic trimethylsilyl chloride.
7. a kind of preparation method of the graphene oxide composite nano filter membrane with ion selectivity separation, which is characterized in that including；
(1) prepared by Polymer interlayers：Non-woven fabrics supporting layer diaphragm is chosen, polymer feed liquid is homogeneously applied to the nonwoven
The surface of cloth supporting layer diaphragm, by adjust the distance between coating head and non-woven fabrics supporting layer diaphragm and polymer feed liquid into
Doses adjusts the thickness of non-woven fabrics supporting layer, and passing through gel slot, rinse bath, quenching tank later keeps the non-woven fabrics supporting layer diaphragm clear
It washes and shapes, obtain the counterdie of Polymer interlayers；
(2) prepared by the nanoscale separating layer of functionalization：Water phase containing graphene oxide is ultrasonically treated, aqueous phase solution is made
The single-side impregnated aqueous phase solution 5S-20min of the counterdie of the Polymer interlayers is purged removal institute by uniformly mixing by air knife
The surface water phase of the counterdie of Polymer interlayers is stated, forms one layer of aqueous solution film on the counterdie of the Polymer interlayers, then
5s-1min will be kept in organic phase solution of the counterdie dipping containing pyromellitic trimethylsilyl chloride of Polymer interlayers, is made by baking oven
With oil phase interface polymerization reaction setting time occurs for water phase, obtains the graphene oxide composite nanometer filter that there is ion selectivity to detach
Film.
8. the graphene oxide composite nano filter membrane according to claim 7 with ion selectivity separation, which is characterized in that
The counterdie of the Polymer interlayers of preparation is soaked in deionized water and is stayed with spare.
9. the graphene oxide composite nano filter membrane according to claim 7 with ion selectivity separation, which is characterized in that
The temperature of the baking oven is 60-110 DEG C, and optimum temperature is 80 DEG C, and the setting time is 1-5min.
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| CN109876666A (en) * | 2019-03-19 | 2019-06-14 | 暨南大学 | A kind of polyamide-graphene oxide composite film and its preparation method and application |
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