WO2018205290A1 - 一种基于 MXene 的复合纳滤膜及其制备方法 - Google Patents
一种基于 MXene 的复合纳滤膜及其制备方法 Download PDFInfo
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- WO2018205290A1 WO2018205290A1 PCT/CN2017/084634 CN2017084634W WO2018205290A1 WO 2018205290 A1 WO2018205290 A1 WO 2018205290A1 CN 2017084634 W CN2017084634 W CN 2017084634W WO 2018205290 A1 WO2018205290 A1 WO 2018205290A1
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- Prior art keywords
- mxene
- membrane
- composite nanofiltration
- nanofiltration membrane
- chloride
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- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims description 27
- 239000002346 layers by function Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 239000006259 organic additive Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- -1 triiron tetroxide Chemical compound 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ROAHTDNKJAHEOL-UHFFFAOYSA-N [Fe].[Co].[Sm] Chemical compound [Fe].[Co].[Sm] ROAHTDNKJAHEOL-UHFFFAOYSA-N 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 claims 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00416—Inorganic membrane manufacture by agglomeration of particles in the dry state by deposition by filtration through a support or base layer
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- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
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- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
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- B01D67/0093—Chemical modification
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- 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
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- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
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- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
- B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
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- B01D71/0211—Graphene or derivates thereof
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- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2323/00—Details relating to membrane preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2325/52—Crystallinity
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- 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
Definitions
- the invention belongs to the technical field of membrane separation, and particularly relates to a composite separation membrane suitable for seawater desalination, brackish water desalination, organic solvent-containing wastewater and heavy metal ion removal.
- Nanofiltration membrane technology is a new energy-saving and environmentally-friendly separation technology.
- the positive-charged nanofiltration membrane has been widely studied because it is more suitable for heavy metal ion removal, high-priced inorganic salt separation and good anti-pollution and anti-bacterial properties.
- MXene is a novel two-dimensional carbide crystal Ti 3 C 2 Tx obtained by ternary layered carbide (representative of Ti 3 AlC 2 ) and stripped by hydrofluoric acid (T stands for -F and - OH and other functional groups). To emphasize that they are stripped from the MAX phase and have a two-dimensional structure similar to Graphene, they are collectively named MXene.
- the material has good film forming properties, remarkable thermal stability and chemical stability, and is a unique separation membrane material.
- the MXene separation membrane can be prepared on the support to obtain a high-performance composite separation membrane, which can be used in water treatment fields such as high temperature, strong acid and alkali, and strong oxidation.
- the object of the present invention is to overcome the deficiencies of the prior art and to provide an easy to prepare MXene A composite membrane that separates materials.
- the porous ceramic membrane, the porous glass membrane, the porous stainless steel membrane, and the like prepared by the method are support layers, MXene
- a composite nanofiltration membrane is obtained by dip coating on the support film.
- the composite nanofiltration membrane was obtained by high temperature crosslinking treatment.
- the invention contributes to greatly simplifying the nanofiltration and reverse osmosis preparation steps, and at the same time improving the use stability of the composite membrane, thereby facilitating the scale application of the special separation occasion.
- the composite nanofiltration membrane is a flat membrane comprising a support layer and a separation functional layer, and the support layer is located below the separation functional layer;
- the separation functional layer is an ultra-thin dense film formed by MXene and a crosslinking agent, and the ultra-thin dense film has a thickness of 50 micrometers or less;
- the crosslinking agent used is glutaraldehyde, epichlorohydrin, epoxypropyltrimethylammonium chloride, trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride or Adipyl chloride;
- the support layer is one of cellulose derivative, polysulfone, polyethersulfone, polyphenylsulfone, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polyimide and polyetherimide. Formed by a mixture of two or more types, the thickness is 50 ⁇ 500 ⁇ m, pore size is 0 ⁇ 100nm.
- the ultra-thin dense film also includes inorganic nano-additives and/or organic additives.
- the inorganic nano additive is one or a mixture of two or more of nano silica, alumina, titania, triiron tetroxide, samarium cobalt iron, molecular sieve, graphene, and inorganic salt; Chitosan quaternary ammonium salt, cellulose quaternary ammonium salt, cellulose acetate, polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, polyvinylidene fluoride, polydimethyldiallyl ammonium chloride, poly One or a mixture of two or more kinds of sodium acrylate is mixed.
- the support layer is replaced by a polymer support film or an inorganic porous film.
- a preparation method of the MXene-based composite nanofiltration membrane is as follows:
- the mass percentage concentration of the aluminum carbonitride is 5-20 wt%; the prepared dispersion A is centrifuged, washed, filtered, and dried to obtain a MXene material;
- the prepared MXene material is added to dimethyl sulfoxide for ultrasonic stripping, and inorganic nano-additive and // Or an organic additive to obtain a dispersion B; the ultrasonic time is 2-12h, wherein the mass concentration of the MXene material is 1 wt% - 5 wt%, the inorganic nano additive and / Or the mass concentration of the organic additive is 0-2 wt %;
- the support layer is used as a filter membrane, and the dispersion B prepared in the step (1) is diluted with water, and then subjected to suction filtration or pressure filtration on the support layer to form a thickness of 50.
- the prepared MXene-based composite nanofiltration membrane is immersed in a solution containing a crosslinking agent, wherein the mass percentage of the crosslinking agent is 0.1 ⁇ 2wt%; heat treatment after removal, heat treatment temperature is 20-100 ° C, heat treatment time is 2-30min, which is a stable MXene-based composite nanofiltration membrane.
- the aluminum carbonitride is replaced by Nb 2 AlC , V 2 Al 2 C or Ti 3 AlC 2 .
- the composite nanofiltration membrane prepared by the present invention is a flat membrane. Due to the use of a novel in the preparation process of its functional layer MXene The material makes the prepared composite membrane have good separation performance, heat resistance and chemical stability, and broadens the scope of its application. It can be applied to the treatment of wastewater containing heavy metal ions, wastewater containing organic solvents and other strong oxidizing properties. Treatment of wastewater.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- the prepared MXene material is added to dimethyl sulfoxide for ultrasonic stripping, and a certain additive is added to obtain a dispersion B, wherein the ultrasonic time is 2-12h, wherein the mass percentage concentration of the dispersoid MXene is 1wt%, and the total mass percentage concentration of the additive nano-silica and carboxymethyl cellulose is 0.5wt%;
- Dispersing liquid B prepared in the step (1) using a polymer supporting film or an inorganic porous film as a filter film After dilution with water, suction filtration or pressure filtration is performed to form a separation functional layer of a certain thickness on the filter membrane; and then subjected to air drying, purging or heat treatment to obtain a composite nanofiltration membrane.
- the treatment solution is a 1 g/L magnesium chloride solution.
- the separation ratio of the separation membrane to the inorganic salt magnesium chloride is 96%, and the water flux can reach 10 L/m 2 h.
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- the prepared MXene material was added to dimethyl sulfoxide for ultrasonic stripping to obtain a dispersion B, wherein the ultrasonic time was 2-12 h.
- the mass percentage concentration of the dispersoid MXene is 3 wt%;
- Dispersing liquid B prepared in the step (1) using a polymer supporting film or an inorganic porous film as a filter film After dilution with water, suction filtration or pressure filtration is performed to form a separation functional layer of a certain thickness on the filter membrane; and then subjected to air drying, purging or heat treatment to obtain a composite nanofiltration membrane.
- the treatment solution is a 1 g/L magnesium chloride solution.
- the separation rate of the separation membrane to the inorganic salt magnesium chloride is 92%, and the water flux can reach 12 L/m 2 h.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Electrochemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
一种基于MXene的复合纳滤膜及其制备方法,该复合纳滤膜为平板膜,包括支撑层和分离功能层,支撑层位于分离功能层下方;分离功能层为由MXene和交联剂形成的超薄致密膜,超薄致密膜厚度为50微米以内。该本制备方法制备过程采用一种新的MXene材料,制得的复合纳滤膜具有良好的分离功能、耐热性能和化学稳定性。
Description
技术领域
本发明属于膜分离技术领域,尤其涉及一种适用于海水淡化、苦咸水脱盐、含有机溶剂废水和重金属离子脱除的复合分离膜。
背景技术
纳滤膜技术是一种节能环保的新型分离技术,其中荷正电纳滤膜由于更适用于重金属离子脱除、高价无机盐分离和良好的抗污染和抗菌性能而得到了广泛的研究。 MXene
是一种由三元层状碳化物(代表性的有 Ti3AlC2 ),经氢氟酸剥离得到的一种新型的二维碳化物晶体
Ti3C2Tx ( T 代表 -F 和 -OH 等官能团)。为了强调它们是由 MAX 相剥离而来,并具有与石墨烯(
Graphene )类似的二维结构,将它们统一命名 MXene 。
该材料成膜性能良好,且具有显著的热稳定性、化学稳定性,是一种独特的分离膜材料。将其在支撑体上制备 MXene
分离膜可以获得高性能的复合分离膜,并可以用于高温、强酸碱、强氧化等水处理领域。
发明内容
本发明的目的在于克服现有技术的不足,提供一种易于制备的以 MXene
为分离材料的复合膜。以商品化的高分子如聚砜、聚醚砜、聚苯砜、聚丙烯腈、聚氯乙烯、聚偏氟乙烯、醋酸纤维素等采用相转化法制备复合膜的支撑层,或是以烧结法制备的多孔陶瓷膜、多孔玻璃膜、多孔不锈钢膜等为支撑层,以
MXene
为分离层膜材料,在支撑膜上采用浸涂法获得复合纳滤膜。并通过高温交联处理得到了复合纳滤膜。本发明有助于大大简化纳滤和反渗透制备步骤,同时提高复合膜的使用稳定性,从而有助于实现特殊分离场合的规模化应用。
本发明的技术方案:
一种基于 MXene
的复合纳滤膜,所述的复合纳滤膜为平板膜,包括支撑层和分离功能层,支撑层位于分离功能层下方;
所述的分离功能层为由 MXene 和交联剂形成的超薄致密膜,超薄致密膜厚度为 50 微米 以内;
所使用的交联剂为戊二醛、环氧氯丙烷、环氧丙基三甲基氯化铵、均苯三甲酰氯、邻苯二甲酰氯、间苯二甲酰氯、对苯二甲酰氯或己二酰氯;
所述的支撑层为由纤维素系列衍生物、聚砜、聚醚砜、聚苯砜、聚丙烯腈、聚氯乙烯、聚偏氟乙烯、聚酰亚胺和聚醚酰亚胺中的一种或两种以上混合形成的,其厚度为 50 ~
500μm ,孔径为 0 ~ 100nm 。
所述的超薄致密膜中还包括无机纳米添加剂和 / 或有机添加剂。
所述的无机纳米添加剂为纳米氧化硅、氧化铝、氧化钛、四氧化三铁、镧锶钴铁、分子筛、石墨烯、无机盐中的一种或两种以上混合;所述的有机添加剂为壳聚糖季铵盐、纤维素季铵盐、醋酸纤维素、聚乙烯醇、聚乙二醇、羧甲基纤维素、聚偏氟乙烯、聚二甲基二烯丙基氯化铵、聚丙烯酸钠中的一种或两种以上混合。
所述的支撑层由高分子支撑膜或无机多孔膜替换。
一种所述的基于 MXene 的复合纳滤膜的制备方法,步骤如下:
(1) 制备分离功能层所用的 MXene 材料
将碳钛化铝缓慢加入到质量百分比浓度为 50%HF 的水溶液中,快速搅拌,经过 12 小时,得到分散液 A
;其中,碳钛化铝的质量百分比浓度为 5-20wt %;将制备的分散液 A 进行离心分离、洗涤、过滤、烘干,得到 MXene 材料;
将制备的 MXene 材料加入二甲基亚砜中进行超声剥离,并加入无机纳米添加剂和 /
或有机添加剂,得到分散液 B ;超声时间为 2-12h ,其中, MXene 材料的质量百分比浓度为 1 wt %-5 wt % ,无机纳米添加剂和 /
或有机添加剂的质量百分比浓度为 0-2 wt % ;
(2) 制备复合纳滤膜的分离功能层
支撑层作为滤膜,将步骤( 1 )制备的分散液 B 用水稀释后,进行抽滤或压滤在支撑层上,形成厚度为 50
微米 以内的分离功能层;稀释后的分散液 B 中 MXene 的质量百分比浓度为 0.1 wt %-2 wt % ,无机纳米添加剂和 /
或有机添加剂的质量百分比浓度为 0-2 wt % ;抽滤或压滤形成的膜经风干、吹扫或热处理后,得到基于 MXene 的复合纳滤膜;
(3) 制备好的基于 MXene 的复合纳滤膜再浸入到含有交联剂溶液中,其中,交联剂的质量百分比浓度
0.1 ~ 2wt %;取出后进行热处理,热处理温度为 20-100℃ ,热处理时间为 2-30min ,即得稳定的基于 MXene 的复合纳滤膜。
所述的碳钛化铝由 Nb2AlC 、
V2Al2C 或 Ti3AlC2 代替。
本发明的有益效果:本发明所制备的复合纳滤膜是一种平板膜。由于其功能层中制备过程中采用了一种新颖的
MXene
材料,使得制备的复合膜具有良好的分离性能、耐热性能和化学稳定性,拓宽了其使用范围,可以应用于含有重金属离子废水的处理,含有机溶剂的废水以及其他具有较强氧化性的废水的处理。
具体实施方式
以下结合技术方案,进一步说明本发明的具体实施方式。
实施例一:
(1) 分离膜用分散液的制备:
将制备的 MXene 材料加入二甲基亚砜中进行超声剥离,并加入一定的添加剂得到分散液 B ,其中超声时间为
2-12h ,其中,分散质 MXene 的质量百分比浓度为 1wt% ,添加剂纳米氧化硅和羧甲基纤维素的总质量百分比浓度 0.5wt% ;
( 2 )制备复合纳滤膜的分离功能层
将高分子支撑膜或无机多孔膜作为滤膜,将步骤( 1 )制备的分散液 B
用水稀释后进行抽滤或压滤,在滤膜上形成一定厚度的分离功能层;再经风干、吹扫或热处理后得到复合纳滤膜。
后浸入到 1% 的戊二醛溶液中 10 秒,取出烘干 60 ℃,时间为 5min 。
(3) 应用:
处理溶液为 1g/L 的氯化镁溶液,在外压为 0.3MPa 时,分离膜对无机盐氯化镁的截留率为 96
%,水通量可达 10L/m2h 。
实施例二:
(1) 分离膜用分散液的制备:
将制备的 MXene 材料加入二甲基亚砜中进行超声剥离,得到分散液 B ,其中超声时间为 2-12h
,其中,分散质 MXene 的质量百分比浓度为 3wt% ;
( 2 )制备复合纳滤膜的分离功能层
将高分子支撑膜或无机多孔膜作为滤膜,将步骤( 1 )制备的分散液 B
用水稀释后进行抽滤或压滤,在滤膜上形成一定厚度的分离功能层;再经风干、吹扫或热处理后得到复合纳滤膜。
后浸入到 0.5% 的 间苯二甲酰氯 溶液中 10 秒,取出烘干 60 ℃,时间为 5min 。
(3) 应用:
处理溶液为 1g/L 的氯化镁溶液,在外压为 0.3MPa 时,分离膜对无机盐氯化镁的截留率为 92
%,水通量可达 12L/m2h 。
Claims (6)
- 一种基于 MXene 的复合纳滤膜,其特征在于,所述的复合纳滤膜为平板膜,包括支撑层和分离功能层,支撑层位于分离功能层下方;所述的分离功能层为由 MXene 和交联剂形成的超薄致密膜,超薄致密膜厚度为 50 微米 以内;所使用的交联剂为戊二醛、环氧氯丙烷、环氧丙基三甲基氯化铵、均苯三甲酰氯、邻苯二甲酰氯、间苯二甲酰氯、对苯二甲酰氯或己二酰氯;所述的支撑层为由纤维素系列衍生物、聚砜、聚醚砜、聚苯砜、聚丙烯腈、聚氯乙烯、聚偏氟乙烯、聚酰亚胺、聚醚酰亚胺中的一种或两种以上混合形成的,其厚度为 50 ~ 500μm ,孔径为 0 ~ 100nm 。
- 根据权利要求 1 所述的基于 MXene 的复合纳滤膜,其特征在于,所述的超薄致密膜中还包括无机纳米添加剂和 / 或有机添加剂。
- 根据权利要求 2 所述的基于 MXene 的复合纳滤膜,其特征在于,所述的无机纳米添加剂为纳米氧化硅、氧化铝、氧化钛、四氧化三铁、镧锶钴铁、分子筛、石墨烯、无机盐中的一种或两种以上混合;所述的有机添加剂为壳聚糖季铵盐、纤维素季铵盐、醋酸纤维素、聚乙烯醇、聚乙二醇、羧甲基纤维素、聚偏氟乙烯、聚二甲基二烯丙基氯化铵、聚丙烯酸钠中的一种或两种以上混合。
- 根据权利要求 3 所述的基于 MXene 的复合纳滤膜,其特征在于,所述的支撑层由高分子支撑膜或无机多孔膜替换。
- 一种权利要求 2~4 所述的基于 MXene 的复合纳滤膜的制备方法,其特征在于,步骤如下:(1) 制备分离功能层所用的 MXene 材料将碳钛化铝缓慢加入到质量百分比浓度为 50%HF 的水溶液中,快速搅拌,经过 12 小时,得到分散液 A ;其中,碳钛化铝的质量百分比浓度为 5-20wt %;将制备的分散液 A 进行离心分离、洗涤、过滤、烘干,得到 MXene 材料;将制备的 MXene 材料加入二甲基亚砜中进行超声剥离,并加入无机纳米添加剂和 / 或有机添加剂,得到分散液 B ;超声时间为 2-12h ,其中, MXene 材料的质量百分比浓度为 1 wt %-5 wt % ,无机纳米添加剂和 / 或有机添加剂的质量百分比浓度为 0-2 wt % ;(2) 制备复合纳滤膜的分离功能层支撑层作为滤膜,将步骤( 1 )制备的分散液 B 用水稀释后,进行抽滤或压滤在支撑层上,形成厚度为 50 微米 以内的分离功能层;稀释后的分散液 B 中 MXene 的质量百分比浓度为 0.1 wt %-2 wt % ,无机纳米添加剂和 / 或有机添加剂的质量百分比浓度为 0-2 wt % ;抽滤或压滤形成的膜经风干、吹扫或热处理后,得到基于 MXene 的复合纳滤膜;(3) 制备好的基于 MXene 的复合纳滤膜再浸入到含有交联剂溶液中,其中,交联剂的质量百分比浓度 0.1 ~ 2wt %;取出后进行热处理,热处理温度为 20-100℃ ,热处理时间为 2-30min ,即得稳定的基于 MXene 的复合纳滤膜。
- 根据权利要求 5 所述的制备方法,其特征在于,所述的碳钛化铝由 Nb2AlC 、 V2Al2C 或 Ti3AlC2 代替。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105271230A (zh) * | 2015-10-27 | 2016-01-27 | 河南理工大学 | 一种多孔Ti3C2/g-C3N4复合薄膜材料的制备方法 |
CN105597567A (zh) * | 2016-03-18 | 2016-05-25 | 郑州大学 | 一种有机无机杂化耐溶剂纳滤复合膜及其制备方法 |
CN106178979A (zh) * | 2016-08-31 | 2016-12-07 | 华南理工大学 | 高性能二维层状Ti3C2‑MXene膜及其制备方法与在水处理中的应用 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1534635A1 (en) * | 2002-09-04 | 2005-06-01 | Biolab, Inc. | Disinfection of reverse osmosis membrane |
KR20090104007A (ko) * | 2007-01-24 | 2009-10-05 | 쿠리타 고교 가부시키가이샤 | 역침투막 처리 방법 |
US20150321147A1 (en) * | 2014-05-08 | 2015-11-12 | Lockheed Martin Corporation | Stacked two-dimensional materials and methods for producing structures incorporating same |
CN103611432B (zh) * | 2013-12-17 | 2016-03-09 | 哈尔滨工业大学 | 一种聚合物/石墨烯纳米复合膜的制备方法 |
HK1207250A2 (zh) * | 2014-10-15 | 2016-01-22 | 新照明設計有限公司 號 | 封裝用基板、立體 封裝、具有該立體 封裝的燈泡及其製作方法 |
AU2016303048A1 (en) * | 2015-08-05 | 2018-03-01 | Lockheed Martin Corporation | Perforatable sheets of graphene-based material |
KR20180037991A (ko) * | 2015-08-06 | 2018-04-13 | 록히드 마틴 코포레이션 | 그래핀의 나노 입자 변형 및 천공 |
WO2017180138A1 (en) * | 2016-04-14 | 2017-10-19 | Lockheed Martin Corporation | Healing of thin graphenic-based membranes via charged particle irradiation |
CN106552514A (zh) * | 2016-11-11 | 2017-04-05 | 北京碧水源膜科技有限公司 | 一种一体式智能净水龙头专用复合纳滤膜及其制备方法 |
WO2018112499A1 (en) * | 2016-12-20 | 2018-06-28 | Monash University | Reverse osmosis membrane and method of use |
CN107029562B (zh) * | 2017-05-12 | 2020-04-07 | 大连理工大学 | 一种基于MXene的复合纳滤膜及其制备方法 |
WO2019089687A1 (en) * | 2017-10-31 | 2019-05-09 | Georgia Tech Research Corporation | Hybrid membranes and methods of making and use thereof |
-
2017
- 2017-05-12 CN CN201710327602.1A patent/CN107029562B/zh active Active
- 2017-05-17 US US16/310,679 patent/US10919000B2/en active Active
- 2017-05-17 WO PCT/CN2017/084634 patent/WO2018205290A1/zh active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105271230A (zh) * | 2015-10-27 | 2016-01-27 | 河南理工大学 | 一种多孔Ti3C2/g-C3N4复合薄膜材料的制备方法 |
CN105597567A (zh) * | 2016-03-18 | 2016-05-25 | 郑州大学 | 一种有机无机杂化耐溶剂纳滤复合膜及其制备方法 |
CN106178979A (zh) * | 2016-08-31 | 2016-12-07 | 华南理工大学 | 高性能二维层状Ti3C2‑MXene膜及其制备方法与在水处理中的应用 |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110449032A (zh) * | 2019-07-08 | 2019-11-15 | 西安建筑科技大学 | 一种耐溶胀二维SA-MXene层状纳滤膜、制备及应用 |
US20210171369A1 (en) * | 2019-12-05 | 2021-06-10 | Battelle Energy Alliance, Llc | Methods of removing contaminants from a solution, and related systems |
CN113019137A (zh) * | 2021-03-12 | 2021-06-25 | 北京化工大学常州先进材料研究院 | MXene@COF复合膜的制备及其应用 |
CN113019137B (zh) * | 2021-03-12 | 2022-09-02 | 北京化工大学常州先进材料研究院 | MXene@COF复合膜的制备及其应用 |
CN114272766A (zh) * | 2022-01-04 | 2022-04-05 | 成都理工大学 | 一种二维MXene基油水分离膜及其制备方法 |
CN114272766B (zh) * | 2022-01-04 | 2023-04-14 | 成都理工大学 | 一种二维MXene基油水分离膜及其制备方法 |
CN114618325A (zh) * | 2022-03-14 | 2022-06-14 | 德蓝水技术股份有限公司 | 一种复合纳滤膜及其制备方法 |
CN114672992A (zh) * | 2022-03-21 | 2022-06-28 | 苏州经贸职业技术学院 | 一种功能持久型棉织物及其制备方法 |
CN114672992B (zh) * | 2022-03-21 | 2023-08-22 | 苏州经贸职业技术学院 | 一种功能持久型棉织物及其制备方法 |
CN116212660A (zh) * | 2023-03-13 | 2023-06-06 | 大连理工大学 | 一种用于染料/盐分离的全粘土棒涂膜的制备方法及应用 |
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