CN112221353B - Polyelectrolyte compound nanofiltration membrane and preparation method and application thereof - Google Patents
Polyelectrolyte compound nanofiltration membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 93
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 55
- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title description 2
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 5
- 239000007888 film coating Substances 0.000 claims abstract description 4
- 238000009501 film coating Methods 0.000 claims abstract description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 14
- 229920000620 organic polymer Polymers 0.000 claims description 10
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 239000003651 drinking water Substances 0.000 claims description 2
- 235000020188 drinking water Nutrition 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 14
- 210000004379 membrane Anatomy 0.000 description 35
- 230000004907 flux Effects 0.000 description 9
- 238000001338 self-assembly Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960002009 naproxen Drugs 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of nanofiltration membranes, and particularly relates to a polyelectrolyte composite nanofiltration membrane as well as a preparation method and application thereof. The method comprises the following steps: 1) preparing a polymer solution; 2) adding polyanion electrolyte into the polymer solution, dissolving, standing and defoaming to obtain a coating solution; 3) preparing a polycation electrolyte solution; 4) coating the film coating liquid on non-woven fabrics, and then immersing the non-woven fabrics in deionized water for curing to obtain a nanofiltration membrane base film; 5) and attaching the polycation electrolyte solution to the nanofiltration membrane base membrane, reacting, and sequentially performing soaking treatment and high-temperature heating treatment on the glycerol aqueous solution after the reaction is finished to obtain the polyelectrolyte composite nanofiltration membrane. According to the technical scheme, polyanionic electrolyte is introduced into a film forming material of the nanofiltration membrane base film, and then polycationic electrolyte is combined with negative charge groups on the surface of the base film to form the polyelectrolyte nanofiltration membrane with the ion pair structure and the compact and ultrathin selective separation layer.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membranes, and particularly relates to a polyelectrolyte composite nanofiltration membrane as well as a preparation method and application thereof.
Background
In recent years, the problem of wastewater treatment has been highlighted. Most of the wastewater contains a large amount of harmful substances which are difficult to degrade, and the harmful substances are discharged into the natural environment without treatment, so that the harmful substances can cause serious harm to human beings and the whole ecology. In response to this problem, membrane separation technology has been gradually applied to the field of wastewater treatment, and at the same time, has shown its wide development prospect.
The separation capacity of the nanofiltration membrane is between that of an ultrafiltration membrane and a reverse osmosis membrane, organic micromolecule substances with the molecular weight of 200-1000-fold and divalent ions can be effectively separated, and the nanofiltration membrane has the characteristics of high separation precision, charged surface, low energy consumption, environmental friendliness and the like. Among them, the charge property is one of the most important features of the nanofiltration membrane, which is also a preparation method of the nanofiltration membrane, namely a layer-by-layer self-assembly preparation principle, which is widely researched. Layer-by-layer self-assembly was first proposed in 1991 by Dexher, university of Mainz, Germany, on the principle ofThe polyelectrolyte with positive charge and negative charge is repeatedly contacted and adsorbed on the solid surface, so that a multi-layer self-assembled membrane is repeatedly formed, and the method is proved to be a method for preparing the nanofiltration membrane with good separation performance. Wanqin Jin, Ali Toutianoush et al [ Jin Wanqin, Toutianoush A, Tieke B. Langmuir,2005,21:10587-]Prepared PVA/PVS nanofiltration membrane (membrane flux 0.7L/(m) 2 H), salt rejection 100%) under similar operating conditions, the flux was much less than that of Brian W.Stanton [ Stanton B W, Harris J J, Miller M D, et al Langmuir,2003,19:7038-]PSS/PAH nanofiltration membrane (membrane flux 50L/(m) 2 H), salt rejection 96%). The main reason for such a large difference in flux is that the self-assembled layer number of the former is as high as 60 bilayers and much higher than 4.5 bilayers of the latter. The increase of the number of the assembling layers can reduce the defects of the nanofiltration membrane, thereby achieving good separation performance, but also leading to factors such as fussy preparation process, long time consumption and the like which are not beneficial to popularization and application.
A polyelectrolyte composite nanofiltration membrane aims to form a multi-component system with a unique ionic cross-linking structure on a solution or solid interface by utilizing polycation and polyanion electrolyte, and can form a dense selective separation layer on the surface of the membrane through one-time reaction. Compared with the traditional layer-by-layer self-assembly, the polyelectrolyte composite nanofiltration membrane has the development potential of solving the problems of more assembly layers and complex process.
Disclosure of Invention
In order to overcome the defects of the prior art and overcome the defects of complex preparation process and low flux caused by excessive layers of traditional layer-by-layer self-assembly, the invention provides a polyelectrolyte composite nanofiltration membrane and a preparation method and application thereof. The invention utilizes polycation and polyanion electrolyte to form a multi-component system with a unique ionic crosslinking structure on a solution or solid interface, and a compact selective separation layer is formed on the surface of the membrane through one-time reaction. Compared with the traditional layer-by-layer self-assembly, the polyelectrolyte composite nanofiltration membrane provided by the invention has the development potential of solving the problems of multiple assembly layers and complex process.
The technical scheme provided by the invention is as follows:
a preparation method of a polyelectrolyte complex nanofiltration membrane comprises the following steps:
1) preparing a polymer solution comprising an organic polymer and an organic solvent, with the organic polymer as a film-forming material;
2) adding polyanion electrolyte into the polymer solution obtained in the step 1), dissolving, standing and defoaming to obtain a coating solution;
3) preparing a solution of a polycation electrolyte;
4) coating the film coating liquid obtained in the step 2) on a non-woven fabric, and then immersing the non-woven fabric in deionized water for curing to obtain a nanofiltration membrane base film;
5) and (3) attaching the polycation electrolyte solution obtained in the step (3) to the nanofiltration membrane base membrane obtained in the step (4), reacting, and sequentially performing soaking treatment and high-temperature heating treatment on a glycerol aqueous solution after the reaction is finished to obtain the polyelectrolyte composite nanofiltration membrane.
According to the technical scheme, polyanionic electrolyte is introduced into a film forming material of the nanofiltration membrane base film, and then the polycationic electrolyte is combined with negative charge groups on the surface of the base film to form a compact and ultrathin selective separation layer. The method can be obtained by one-time self-assembly.
Specifically, in the step 1), the mass percentage of the solute in the polymer solution is 14-20%.
Specifically, in the step 1), the organic solvent is any one of N-N dimethylacetamide, N-N dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
Specifically, in the step 1), the organic polymer is selected from any one of polyethersulfone, polysulfone or polyacrylonitrile.
Specifically, in the step 2), the mass ratio of the polyanionic electrolyte to the organic polymer is 1 (8-35).
Specifically, in step 2), the polyanionic electrolyte is selected from any one of sulfonated polyether ether ketone, hydrolyzed polyacrylonitrile or sulfonated polysulfone.
Specifically, in step 3), the solvent of the polycationic electrolyte is any one of water, methanol, ethanol or isopropanol.
Specifically, in the step 3), the mass percentage of the solute of the aqueous solution of the polycation electrolyte is 0.5-1%.
Specifically, in step 3), the polycationic electrolyte is selected from any one of polyethyleneimine or dopamine.
Specifically, in the step 3), the thickness of the coating solution on the non-woven fabric is 200-300 μm.
Specifically, in the step 5):
the reaction time is 10-60 min;
the mass percentage of the aqueous solution of the glycerol is 5-20%, and the soaking time is 10-30 min;
the temperature of the high-temperature heating treatment is 80-120 ℃, and the time is 10-15 min;
specifically, the preparation method of the polyelectrolyte composite nanofiltration membrane comprises the following steps:
A) dissolving an organic polymer serving as a film forming material in an organic solvent to prepare a polymer solution with the mass percentage of 14-20 wt%, and standing for later use;
B) adding a polyanionic electrolyte into the solution prepared in the step A), wherein the mass ratio of the adding amount of the polyanionic electrolyte to the organic polymer in the step A) is 1: (8-35), stirring to dissolve, standing and defoaming to obtain a coating solution;
C) preparing the polycation electrolyte into a solution with the mass percentage of 1%, and standing for later use;
D) pouring the film coating liquid in the step B) onto a non-woven fabric support, uniformly coating the organic solution on the non-woven fabric by using a film scraping knife, then quickly immersing in deionized water for curing to obtain a nanofiltration membrane base film, and standing for later use;
E) pouring the aqueous solution obtained in the step C) on the surface of the basement membrane to enable the polyelectrolyte with opposite charges to generate a cross-linking reaction, and performing post-treatment to obtain the polyelectrolyte composite nanofiltration membrane.
The invention also provides the polyelectrolyte composite nanofiltration membrane prepared by the preparation method.
The invention also provides application of the polyelectrolyte composite nanofiltration membrane, which is used for removing dye in sewage treatment or removing organic matters in drinking water treatment.
Preferably, the molecular weight of the dye or organic matter in the water used for removal is 500-2000. With a high rejection rate for this range of organics.
Aiming at the defect that the preparation process of the traditional layer-by-layer self-assembly method is complicated, the polyelectrolyte is introduced into the composite nanofiltration membrane to serve as the ultrafiltration base membrane of the support body, so that the ultrafiltration base membrane is modified, the surface of the base membrane is charged and reacts with the polyelectrolyte with opposite charges, a compact selective layer is directly formed on the surface of the support membrane, the dense selective layer is only equivalent to half of a double layer formed by combining two polyelectrolytes in the layer-by-layer self-assembly, the membrane thickness is greatly reduced, and the membrane flux is increased. The ionic crosslinking among polyelectrolytes and the strengthening of the post treatment on the crosslinking effect enable the nanofiltration membrane to have good stability. The separation performance of the nanofiltration membrane can be controlled by adjusting the concentration of the polymers and the concentration ratio among the polymers, the reaction time and various parameters of post-treatment so as to adapt to different separation requirements. The method has simple and economic process and wide application range.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
1. Respectively weighing 8g of PES and 1g of SPEEK, adding 41g N-N dimethylacetamide organic solvent, continuously stirring at normal temperature until PES and SPEEK are completely dissolved, and standing and defoaming the solution to obtain coating solution;
2. weighing 1g of PEI to a 250mL volumetric flask, adding deionized water to the scale mark, continuously stirring at normal temperature until the PEI is completely dissolved, and standing the solution for later use;
3. uniformly coating the coating solution on the non-woven fabric by using a non-solvent induced phase separation method and a film scraping knife with the thickness of 250 mu m, quickly immersing the non-woven fabric in deionized water to prepare a base film, and standing for 12 hours for use;
4. taking out the base membrane, cleaning the membrane surface, pouring the PEI solution on the membrane, reacting for 30min, and washing with deionized water to remove the redundant PEI on the membrane surface;
5. soaking the membrane in 5% glycerol water solution for 30 min;
6. and (3) treating the membrane at 120 ℃ for 10min to prepare the polyelectrolyte composite nanofiltration membrane.
The separation performance of the nanofiltration membrane on polyethylene glycol aqueous solution with the average molecular weight of 1000 is measured, when the concentration of polyethylene glycol in the feed liquid is 0.1g/L, the temperature is 25 ℃, the operating pressure is 4bar, and the membrane flux is 56.8L/(m) 2 H) the retention was 99.2%.
Example 2
1. Respectively weighing 7.11g of PES and 0.89g of SPEEK, adding 42g of DMAC organic solvent, continuously stirring at normal temperature until the PES and the SPEEK are completely dissolved, and standing and defoaming the solution to obtain a coating solution;
2. weighing 1g of PEI to a 250mL volumetric flask, adding deionized water to the scale mark, continuously stirring at normal temperature until the PEI is completely dissolved, and standing the solution for later use;
3. uniformly coating the coating solution on the non-woven fabric by using a non-solvent induced phase separation method and a film scraping knife with the thickness of 250 mu m, quickly immersing the non-woven fabric in deionized water to prepare a base film, and standing for 12 hours for use;
4. taking out the base membrane, cleaning the membrane surface, pouring the PEI solution on the membrane, reacting for 30min, and washing with deionized water to remove the redundant PEI on the membrane surface;
5. soaking the membrane in 5% glycerol water solution for 30 min;
6. and (3) treating the membrane at 120 ℃ for 10min to prepare the polyelectrolyte composite nanofiltration membrane.
The separation performance of the nanofiltration membrane on four dyes of rose bengal, congo red, methyl orange and methyl blue is measured, when the conductivity of the aqueous dye solution is 2mS/cm, the temperature is 25 ℃, the operating pressure is 4bar, and the membrane flux is 59.6L/(m) respectively 2 ·h)、56.4L/(m 2 ·h)、54.7L/(m 2 ·h)、13.7L/(m 2 H) retention rates of 99.6%, 99.3%, 96% and 86.4%, respectively.
Example 3
1. Respectively weighing 7.11g of PES and 0.89g of SPEEK, adding 42g of DMAC organic solvent, continuously stirring at normal temperature until the PES and the SPEEK are completely dissolved, and standing and defoaming the solution to obtain a coating solution;
2. weighing 1g of PEI to a 250mL volumetric flask, adding deionized water to the scale mark, continuously stirring at normal temperature until the PEI is completely dissolved, and standing the solution for later use;
3. uniformly coating the coating solution on the non-woven fabric by a non-solvent phase separation method by using a film scraping knife with the thickness of 250 mu m, quickly immersing the non-woven fabric in deionized water to prepare a base film, and standing for 12 hours for use;
4. taking out the base membrane, cleaning the membrane surface, pouring the PEI solution on the membrane, reacting for 30min, and washing with deionized water to remove the redundant PEI on the membrane surface;
5. soaking the membrane in 5% glycerol water solution for 30 min;
6. and (3) treating the membrane at 120 ℃ for 10min to prepare the polyelectrolyte composite nanofiltration membrane.
The separation performance of the nanofiltration membrane obtained in the example on the ibuprofen solution and the naproxen solution is measured, when the drug concentration is 5mg/L, the temperature is 25 ℃, the operation pressure is 4bar, and the membrane flux is 40.6L/(m) 2 H) and 66.7L/(m) 2 H) retention rates of 80.9% and 75.9%, respectively.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the polyelectrolyte composite nanofiltration membrane is characterized by comprising the following steps:
1) preparing a polymer solution comprising an organic polymer and an organic solvent, with the organic polymer as a film-forming material;
2) adding polyanion electrolyte into the polymer solution obtained in the step 1), dissolving, standing and defoaming to obtain a coating solution;
3) coating the film coating liquid obtained in the step 2) on a non-woven fabric, and then immersing the non-woven fabric in deionized water for curing to obtain a nanofiltration membrane base film;
4) attaching a polycation electrolyte solution to the nanofiltration membrane base membrane obtained in the step 3), reacting, and sequentially performing soaking treatment and high-temperature heating treatment on a glycerol aqueous solution after the reaction is finished to obtain a polyelectrolyte composite nanofiltration membrane;
wherein:
the mass percentage of the water solution of the glycerol is 5-20%, and the soaking time is 10-30 min;
the temperature of the high-temperature heating treatment is 80-120 ℃, and the time is 10-15 min.
2. The method for preparing a polyelectrolyte complex nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step 1), the mass percentage of solute in the polymer solution is 14-20%; the organic solvent is any one of N-N dimethyl acetamide, N-N dimethyl formamide, dimethyl sulfoxide or N-methyl pyrrolidone.
3. The method for preparing a polyelectrolyte complex nanofiltration membrane according to claim 2, wherein the method comprises the following steps: the organic polymer is selected from any one of polyether sulfone, polysulfone or polyacrylonitrile.
4. The method for preparing a polyelectrolyte complex nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step 2), the mass ratio of the polyanionic electrolyte to the organic polymer is 1 (8-35).
5. The method for preparing a polyelectrolyte complex nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step 2), the polyanionic electrolyte is selected from any one of sulfonated polyether ether ketone, hydrolyzed polyacrylonitrile or sulfonated polysulfone.
6. The method for preparing a polyelectrolyte complex nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step 4), the solvent of the polycation electrolyte solution is any one of water, methanol, ethanol or isopropanol, and the mass percentage of the solute is 0.1-1%.
7. The method for preparing a polyelectrolyte complex nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step 4), the polycationic electrolyte is selected from any one of polyethyleneimine or dopamine.
8. The method for preparing a polyelectrolyte complex nanofiltration membrane according to any one of claims 1 to 7, wherein in the step 4): the reaction time is 10-60 min.
9. A polyelectrolyte complex nanofiltration membrane prepared according to the preparation method of any one of claims 1 to 8.
10. Use of a polyelectrolyte complex nanofiltration membrane according to claim 9, wherein: used for dye removal in sewage treatment or organic matter removal in drinking water treatment.
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