CN117654304A - Positively charged mixed matrix film doped with etched zinc oxide nano particles and preparation method thereof - Google Patents
Positively charged mixed matrix film doped with etched zinc oxide nano particles and preparation method thereof Download PDFInfo
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- CN117654304A CN117654304A CN202311601123.6A CN202311601123A CN117654304A CN 117654304 A CN117654304 A CN 117654304A CN 202311601123 A CN202311601123 A CN 202311601123A CN 117654304 A CN117654304 A CN 117654304A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 71
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011159 matrix material Substances 0.000 title claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000012071 phase Substances 0.000 claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 26
- 239000004941 mixed matrix membrane Substances 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 18
- 239000008346 aqueous phase Substances 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 8
- 238000004381 surface treatment Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229920002873 Polyethylenimine Polymers 0.000 claims description 13
- 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 9
- 238000012360 testing method Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 241000080590 Niso Species 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 45
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 52
- 239000000243 solution Substances 0.000 description 42
- 238000001728 nano-filtration Methods 0.000 description 7
- 230000035699 permeability Effects 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 230000021148 sequestering of metal ion Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of membrane separation, and discloses a novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles and a preparation method thereof, wherein the method comprises the following steps: preparing etched zinc oxide nano particles; preparing an interfacial polymerized aqueous phase solution and an interfacial polymerized oil phase solution; etching nano-particle doping is carried out on the bottom film by using water; interfacial polymerization is carried out on the oil phase film; performing heat treatment on the membrane subjected to interfacial polymerization to obtain a novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles; and applying the mixed matrix membrane to heavy metal ion removal. The mixed matrix membrane has mild preparation conditions, improved hydrophilicity and electropositivity, excellent performance of separating heavy metal ions and remarkable industrial application value.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a novel positively charged mixed matrix membrane doped with etched zinc oxide nanoparticles and a preparation method thereof.
Background
Heavy metal ions are derived from a variety of natural and man-made sources, such as mining, metallurgical, electroplating, tanning, textile, paper and pesticide industries. These ions can have various adverse effects on human health and the ecosystem. Therefore, it is important to develop an effective and economical method for removing heavy metal ions in wastewater. Conventional treatment methods include chemical precipitation, oxidation, ion exchange, and electrodialysis. However, these methods have some drawbacks such as high cost, low selectivity and the production of toxic sludge or byproducts. Therefore, alternative methods based on membrane technology have been explored in recent years. Membrane technology has shown great potential in removing heavy metal ions because it provides a wide range of membrane properties and separation mechanisms.
Conventional NF membranes are a class of Thin Film Composite (TFC) membranes consisting of a thin selective layer of Polyamide (PA) on a porous support layer. However, TFC membranes typically have negatively charged surfaces, which limit their rejection properties for heavy metal ions. To obtain better separation performance, exploration is generally conducted from two aspects: particle size sieving and the daonan effect. The radius of the hydrated cation of the heavy metal ion isHowever, the nanofiltration membrane has a pore size ranging from 0.5nm to 2nm, and thus cannot use particlesAnd heavy metal ions are effectively separated by a radial screening method. Therefore, the southwest effect plays a key role, and the development of positively charged nanofiltration membranes is an important way to improve the efficiency and selectivity of water treatment. Polyethyleneimine (PEI) is a hydrophilic cationic polyelectrolyte, the preferred amine monomer for the production of positively charged Nanofiltration (NF) membranes. However, PEI/TMC membranes have a relatively weak capacity for treating heavy metal ion wastewater because of the relatively dense selective layer, resulting in a relatively low membrane permeability.
There is a "Trade-off" effect between permeability and selectivity that is difficult to overcome, i.e., selectivity for macromolecular species and permeability for water are difficult to increase simultaneously. Therefore, many studies have added porous materials such as molecular sieves, metal organic frameworks, covalent organic frameworks, graphene, etc. to polymers to prepare Mixed Matrix Membranes (MMMs), and it is desired to improve the separation performance of the membranes. The particle size of the doped particles has a great influence on the properties of the mixed matrix film. The small particle size of the doped particles can increase the specific surface area of the mixed matrix membrane, thereby improving the permeability and selectivity. In addition, the morphology of the filler particles can also affect the performance of the mixed matrix film. Therefore, the invention adopts an alkali etching mode to etch the zinc oxide nano etching particles into a porous structure and dope the zinc oxide nano etching particles into the polyamide layer, overcomes the trade-off of permeation selectivity by providing water channels in the nano particle pores or around the hydrophilic surface, obviously improves the permeability of the TFN film and the interception of heavy metal ions, and obtains the novel positively charged mixed matrix film doped with the etched zinc oxide nano particles.
Disclosure of Invention
Aiming at the problem of low permeability of the traditional positively charged nanofiltration membrane, the invention provides a novel membrane preparation method, and the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles prepared by the method can effectively improve the flux of the membrane and the interception performance of heavy metal ions.
The technical scheme of the invention is as follows:
a preparation method of a positively charged mixed matrix film doped with etched zinc oxide nano particles comprises the following specific steps:
(1) Preparation of etched zinc oxide nano particles: zinc oxide nano-particles are added into an conical flask filled with deionized water, and the particles are uniformly dispersed by ultrasonic waves. KOH is then added and the mixture is quickly transferred into a water bath for heating. After that, the white solid was centrifugally washed with deionized water. Finally, the mixture was dried overnight in a vacuum oven to give a powder.
(2) Aqueous coating of the film: and pouring the aqueous phase solution on the surface of the base film, and blowing off excessive water by an air knife to obtain the primary surface treatment film.
(3) Interfacial polymerization of the film: and pouring the oil phase solution on the surface of the primary surface treatment film, and performing interfacial polymerization reaction to obtain the secondary surface treatment film.
(4) Heat treating the film: and (3) placing the secondary surface treatment film into an oven for heat treatment, and further performing interfacial polymerization to enhance the crosslinking degree to obtain the positively charged mixed matrix film doped with the etched zinc oxide nano particles.
Further, in the step (1), the molar concentration of KOH used for etching is 0.05 to 0.2M, preferably 0.1M, the water bath temperature is 25 to 85 ℃, preferably 85 ℃, and the water bath time is 0.5 to 2 hours, preferably 1 hour.
Further, the zinc oxide used in step (1) has a particle size of 30 to 50nm.
Further, the carrier film needs to be soaked in deionized water for 12 hours before use.
Further, the aqueous solution comprises 10 to 20ml, preferably 10ml, of a polyethyleneimine solution with a mass concentration of 0.05 to 0.2wt.%, preferably 0.1wt.% and 0.005 to 0.02wt.%, preferably 0.01 wt.% of etched zinc oxide nanoparticles, the remainder being deionized water.
Further, the oil phase solution contains 10 to 20mL, preferably 10mL, of trimesoyl chloride in an amount concentration of 0.05 to 0.1wt.%, preferably 0.1wt.%, with the remainder being n-hexane.
Further, in the step (2), the aqueous phase solution is poured onto the surface of the carrier film and allowed to stand for 1 to 2 minutes, preferably 2 minutes.
Further, in the step (3), the oil phase solution is poured onto the surface of the primary surface treatment film, and the solution is left for 10 to 30 seconds, preferably 30 seconds, and then the excess oil phase solution is poured off.
Further, in the step (4), the heat treatment temperature is 60 to 80 ℃, preferably 60 ℃, and the heat treatment time is 2 to 5min, preferably 5min.
Further, the positively charged mixed matrix film doped with etched zinc oxide nanoparticles in step (4) needs to be soaked in deionized water for 12 hours before testing.
Further, the aqueous solution was subjected to ultrasonic treatment for 1 hour to sufficiently disperse the particles.
Further, the bottom membrane is a polysulfone ultrafiltration membrane.
Based on the same inventive concept, the invention also protects the novel positively charged mixed matrix membrane of doped etched zinc oxide nano particles prepared by the method for preparing the positively charged mixed matrix membrane of doped etched zinc oxide nano particles, wherein the novel positively charged mixed matrix membrane of doped etched zinc oxide nano particles is used for heavy metal ion removal experiments of 1000ppm CuSO4, znSO4 and NiSO4 solutions, the flux is 8L h-1m-2bar-1 under the test pressure of 4bar, and the retention rate of heavy metal ions is 95% -96%.
The inventive step of the invention is step (1), the conventional nanoparticle filler such as alumina, titanium dioxide, etc. is the nanoparticle without obvious pore structure, the invention converts the nanoparticle into the porous structure through alkali etching and adds into the polyamide layer, improves the hydrophilicity and electropositivity of the membrane, thus improving the flux and the heavy metal ion retention rate of the mixed matrix membrane.
Compared with the prior art, the invention has the following beneficial technical effects that
(1) According to the invention, the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles is prepared by taking the polysulfone ultrafiltration membrane as a substrate, taking the Polyethyleneimine (PEI), the etched zinc oxide nano particles as a water phase monomer and taking trimesoyl chloride (TMC) as an oil phase solution through an interfacial polymerization method, so that the water flux and the heavy metal ion interception performance are effectively improved under the optimal load.
(2) Polyethyleneimine (PEI) is a hydrophilic cationic polyelectrolyte monomer used to make positively charged NF membranes. The porous zinc oxide nano particles are prepared by a wet alkali etching method, and the novel positively charged mixed matrix membrane doped with the etched zinc oxide nano particles is prepared by interfacial polymerization, so that the electropositivity and the hydrophilicity of the membrane are further improved.
(3) The preparation method is simple, has low cost, and can improve the specific surface area and the porosity of the zinc oxide nano particles without obvious structures, the flux of the membrane and the interception performance of heavy metal ions.
Drawings
FIG. 1 is a scanning electron microscope image of etched zinc oxide nanoparticles in example 3;
FIG. 2 is a scanning electron microscope image (surface view) of a novel positively charged hybrid matrix film doped with etched zinc oxide nanoparticles in example 3;
FIG. 3 is a scanning electron microscope (cross-sectional view) of a novel positively charged hybrid matrix film doped with etched zinc oxide nanoparticles of example 3;
Detailed Description
The following provides a specific embodiment of a preparation method of a novel positively charged mixed matrix film doped with etched zinc oxide nanoparticles.
Example 1
The preparation method of the novel positively charged mixed matrix film doped with etched zinc oxide nano particles comprises the following steps:
(1) Taking a polysulfone ultrafiltration membrane as a bottom membrane, soaking the bottom membrane in deionized water for 12 hours, and airing the bottom membrane until no obvious water drops are formed on the surface of the bottom membrane;
(2) Preparing an aqueous phase solution and an oil phase solution containing etched nano particles with the particle size of 30nm, wherein the aqueous phase solution contains 10ml of polyethyleneimine solution with the mass concentration of 0.1wt% and 0.005 wt% of etched zinc oxide nano particles with the particle size of 30-50nm, and the balance of deionized water; the oil phase solution contains 10mL of trimesoyl chloride with an amount concentration of 0.1wt% and the rest of normal hexane.
(3) Pouring the aqueous phase solution on the surface of a bottom film, standing for 2min, removing excessive water by an air knife to obtain a primary surface treatment film, and fixing the film in a square polytetrafluoroethylene frame;
(4) Pouring the oil phase solution on the surface of the primary surface treatment film, standing for 30sec to perform interfacial polymerization reaction, and removing the oil phase solution to obtain the secondary surface treatment film.
(5) Placing the secondary surface treatment film into an oven for heat treatment at a heating temperature of 60 DEG C O And C, heating for 5min, and further performing interfacial polymerization to enhance the crosslinking degree to obtain the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles.
(6) Immersing the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles prepared in the step (5) in deionized water, and carrying out heavy metal ion interception test.
Example 2
The preparation method of the novel positively charged mixed matrix film doped with etched zinc oxide nano particles comprises the following steps:
(1) Taking a polysulfone ultrafiltration membrane as a bottom membrane, soaking the bottom membrane in deionized water for 12 hours, and airing the bottom membrane until no obvious water drops are formed on the surface of the bottom membrane;
(2) Preparing an aqueous phase solution and an oil phase solution containing etched nano particles with the particle size of 30nm, wherein the aqueous phase solution contains 10ml of polyethyleneimine solution with the mass concentration of 0.1wt% and 0.01 wt% of etched zinc oxide nano particles with the particle size of 30-50nm, and the balance of deionized water; the oil phase solution contains 10mL of trimesoyl chloride with an amount concentration of 0.1wt% and the rest of normal hexane.
(3) Pouring the aqueous phase solution on the surface of a bottom film, standing for 2min, removing excessive water by an air knife to obtain a primary surface treatment film, and fixing the film in a square polytetrafluoroethylene frame;
(4) Pouring the oil phase solution on the surface of the primary surface treatment film, standing for 30sec to perform interfacial polymerization reaction, and removing the oil phase solution to obtain the secondary surface treatment film.
(5) Placing the secondary surface treatment film into an oven for heat treatment at a heating temperature of 60 DEG C O And C, heating for 5min, and further performing interfacial polymerization to enhance the crosslinking degree to obtain the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles.
(6) Immersing the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles prepared in the step (5) in deionized water, and carrying out heavy metal ion interception test.
Example 3
The preparation method of the novel positively charged mixed matrix film doped with etched zinc oxide nano particles comprises the following steps:
(1) Taking a polysulfone ultrafiltration membrane as a bottom membrane, soaking the bottom membrane in deionized water for 12 hours, and airing the bottom membrane until no obvious water drops are formed on the surface of the bottom membrane;
(2) Preparing an aqueous phase solution and an oil phase solution containing etched nano particles with the particle size of 30nm, wherein the aqueous phase solution contains 10ml of polyethyleneimine solution with the mass concentration of 0.1wt% and 0.015 wt% of etched zinc oxide nano particles with the particle size of 30-50nm, and the balance of deionized water; the oil phase solution contains 10mL of trimesoyl chloride with an amount concentration of 0.1wt% and the rest of normal hexane.
(3) Pouring the aqueous phase solution on the surface of a bottom film, standing for 2min, removing excessive water by an air knife to obtain a primary surface treatment film, and fixing the film in a square polytetrafluoroethylene frame;
(4) Pouring the oil phase solution on the surface of the primary surface treatment film, standing for 30sec to perform interfacial polymerization reaction, and removing the oil phase solution to obtain the secondary surface treatment film.
(5) Placing the secondary surface treatment film into an oven for heat treatment at a heating temperature of 60 DEG C O And C, heating for 5min, and further performing interfacial polymerization to enhance the crosslinking degree to obtain the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles.
(6) Immersing the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles prepared in the step (5) in deionized water, and carrying out heavy metal ion interception test.
Example 4
The preparation method of the novel positively charged mixed matrix film doped with etched zinc oxide nano particles comprises the following steps:
(1) Taking a polysulfone ultrafiltration membrane as a bottom membrane, soaking the bottom membrane in deionized water for 12 hours, and airing the bottom membrane until no obvious water drops are formed on the surface of the bottom membrane;
(2) Preparing an aqueous phase solution and an oil phase solution containing etched nano particles with the particle size of 30nm, wherein the aqueous phase solution contains 10ml of polyethyleneimine solution with the mass concentration of 0.1wt% and 0.02 wt% of etched zinc oxide nano particles with the particle size of 30-50nm, and the balance of deionized water; the oil phase solution contains 10mL of trimesoyl chloride with an amount concentration of 0.1wt% and the rest of normal hexane.
(3) Pouring the aqueous phase solution on the surface of a bottom film, standing for 2min, removing excessive water by an air knife to obtain a primary surface treatment film, and fixing the film in a square polytetrafluoroethylene frame;
(4) Pouring the oil phase solution on the surface of the primary surface treatment film, standing for 30sec to perform interfacial polymerization reaction, and removing the oil phase solution to obtain the secondary surface treatment film.
(5) Placing the secondary surface treatment film into an oven for heat treatment at a heating temperature of 60 DEG C O And C, heating for 5min, and further performing interfacial polymerization to enhance the crosslinking degree to obtain the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles.
(6) Immersing the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles prepared in the step (5) in deionized water, and carrying out heavy metal ion interception test.
Comparative example 1
Comparative example 1 differs from example 1 above in that part of the procedure in step 2 was omitted, i.e. no etched zinc oxide nanoparticles were added to the aqueous solution.
The novel positively charged mixed matrix films doped with etched zinc oxide nanoparticles prepared in examples 1-4 and comparative example 1 were used for heavy metal ion retention performance test, and the performance indexes are shown in table 1.
TABLE 1 novel positively charged hybrid matrix film Performance index for etched zinc oxide nanoparticle doped prepared in examples 1-4, comparative example 1
The test can obtain the novel positively charged mixed matrix membrane doped with etched zinc oxide nano particles, which is prepared by the invention, has the entrapment rate of divalent heavy metal ions reaching more than 95% under the optimal load, and the mixed matrix membrane has higher entrapment rate of divalent heavy metal ions.
The foregoing description is merely a preferred embodiment of the present invention and is not intended to be limiting, and it should be noted that modifications can be made to the foregoing embodiments by those skilled in the art without departing from the spirit of the present invention, and such modifications are also to be considered as being within the scope of the present invention.
Claims (10)
1. The preparation method of the positively charged mixed matrix film doped with etched zinc oxide nano particles is characterized by comprising the following steps of:
(1) Preparation of etched zinc oxide nano particles: zinc oxide nano-particles are added into an conical flask filled with deionized water, and the particles are uniformly dispersed by ultrasonic waves; then adding KOH, and transferring into a water bath kettle for heating; then, centrifugally washing the white powder with deionized water; drying overnight in a vacuum oven to obtain powder;
(2) Aqueous coating of the film: pouring the aqueous phase solution on the surface of the base film, and blowing off excessive water by an air knife to obtain a primary surface treatment film;
(3) Interfacial polymerization of the film: pouring the oil phase solution on the surface of the primary surface treatment film, and performing interfacial polymerization reaction to obtain a secondary surface treatment film;
(4) Heat treating the film: and (3) placing the secondary surface treatment film into an oven for heat treatment, and further performing interfacial polymerization to enhance the crosslinking degree to obtain the positively charged mixed matrix film doped with the etched zinc oxide nano particles.
2. The method for preparing the positively charged mixed matrix film doped with etched zinc oxide nano particles according to claim 1, which is characterized in that: the particle size of the zinc oxide nano particles is 30-50nm.
3. The method for preparing the positively charged mixed matrix film doped with etched zinc oxide nano particles according to claim 1, which is characterized in that: in the step (1), the molar concentration of KOH used for etching is 0.05-0.2M, the water bath temperature is 25-85 ℃, and the water bath time is 0.5-2 h.
4. The method for preparing the positively charged mixed matrix film doped with etched zinc oxide nano particles according to claim 1, which is characterized in that: the aqueous phase solution comprises 10-20 ml of polyethyleneimine solution with mass concentration of 0.05-0.2 wt.% and 0.005-0.02 wt.% of etched zinc oxide nano particles, and the balance of deionized water.
5. The method for preparing the positively charged mixed matrix film doped with etched zinc oxide nano particles according to claim 1, which is characterized in that: the oil phase solution contains 10-20 mL of trimesoyl chloride with mass concentration of 0.05-0.1 wt.% and the balance of normal hexane.
6. The method for preparing the positively charged mixed matrix film doped with etched zinc oxide nano particles according to claim 1, which is characterized in that: in the step (2), the aqueous phase solution is poured on the surface of the base film and kept stand for 1-2 min.
7. The method for preparing the positively charged mixed matrix film doped with etched zinc oxide nano particles according to claim 1, which is characterized in that: in the step (3), the oil phase solution is poured onto the surface of the primary surface treatment film, and after standing for 10 to 30sec, the excess oil phase solution is poured off.
8. The method for preparing the positively charged mixed matrix film doped with etched zinc oxide nano particles according to claim 1, which is characterized in that: in the step (4), the heat treatment temperature is 60-80 ℃ and the heat treatment time is 2-5 min.
9. The method for preparing a positively charged mixed matrix film doped with etched zinc oxide nanoparticles according to any one of claims 1 to 8, wherein the method comprises the following steps: the positively charged mixed matrix membrane doped with etched zinc oxide nano particles is used for 1000ppm CuSO 4 、ZnSO 4 And NiSO 4 Heavy metal ion removal experiment of the solution, under the condition of the test pressure of 4bar, the flux of the solution is 8L h -1 m -2 bar -1 The retention rate of heavy metal ions is 95-96%.
10. Use of a positively charged mixed matrix membrane doped with etched zinc oxide nanoparticles prepared according to the method of any one of claims 1 to 10 in the field of heavy metal ion removal.
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