CN114307678A - Preparation method of composite nanofiltration membrane based on zwitterion regulation and control - Google Patents
Preparation method of composite nanofiltration membrane based on zwitterion regulation and control Download PDFInfo
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- CN114307678A CN114307678A CN202210144196.6A CN202210144196A CN114307678A CN 114307678 A CN114307678 A CN 114307678A CN 202210144196 A CN202210144196 A CN 202210144196A CN 114307678 A CN114307678 A CN 114307678A
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- 239000012528 membrane Substances 0.000 title claims abstract description 104
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000033228 biological regulation Effects 0.000 title claims abstract description 16
- -1 polyphenol compound Chemical class 0.000 claims abstract description 33
- 238000000151 deposition Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 5
- 230000003115 biocidal effect Effects 0.000 claims abstract description 3
- 239000003651 drinking water Substances 0.000 claims abstract description 3
- 235000020188 drinking water Nutrition 0.000 claims abstract description 3
- 239000000598 endocrine disruptor Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- 230000008021 deposition Effects 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims description 10
- 229940074360 caffeic acid Drugs 0.000 claims description 10
- 235000004883 caffeic acid Nutrition 0.000 claims description 10
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims description 10
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229940117986 sulfobetaine Drugs 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 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 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000000614 phase inversion technique Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 claims description 4
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 4
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 4
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 238000000108 ultra-filtration Methods 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 229940082044 2,3-dihydroxybenzoic acid Drugs 0.000 claims description 2
- NSWDWUHBMOIGOA-UHFFFAOYSA-N 3,5-diaminobenzenesulfonic acid Chemical compound NC1=CC(N)=CC(S(O)(=O)=O)=C1 NSWDWUHBMOIGOA-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 claims description 2
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 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 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 18
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- QRMLKVVWCJUMPR-UHFFFAOYSA-N BrCC[Na] Chemical compound BrCC[Na] QRMLKVVWCJUMPR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a composite nanofiltration membrane based on zwitterion regulation, belongs to the technical field of membrane separation, and solves the problems of low flux of the nanofiltration membrane and low separation selectivity of multivalent/monovalent inorganic salt. The preparation method of the composite nanofiltration membrane comprises the following steps: firstly preparing a support film, then depositing a zwitterion compound and a polyphenol compound on the support film, then carrying out interfacial polymerization reaction of diamine and polybasic acyl chloride, and finally carrying out heat treatment. The adhesion of the mussel-like polyphenol compound is utilized to promote the stable existence of the zwitterionic compound on the surface of the support membrane, and the strong hydrophilicity and the charge action of the zwitterionic compound are utilized to improve the flux and the separation selectivity of the nanofiltration membrane. The obtained composite nanofiltration membrane has wide application prospects in the aspects of dye removal, inorganic salt interception, multivalent/monovalent inorganic salt separation, antibiotic purification, drinking water purification, endocrine disrupter removal and the like.
Description
Technical Field
The invention relates to a preparation method of a composite nanofiltration membrane based on zwitter-ion regulation and control, and belongs to the technical field of membrane separation.
Background
The nanofiltration membrane is a novel separation membrane which is arranged between the ultrafiltration membrane and the reverse osmosis membrane and takes pressure as driving force, the aperture is about 1nm, and the molecular weight cutoff is between 200 and 1000 Da. Due to the nanoscale pore diameter and the surface with charge property, the nanofiltration membrane can separate monovalent ions from high-valence ions and organic matters with low molecular weight from organic matters with high molecular weight by utilizing the pore diameter screening effect and the charge effect.
At present, the composite nanofiltration membrane prepared by the interfacial polymerization method is most commonly used, the preparation process is mature, but the preparation process is influenced by the Trade-off effect, and the water flux of the composite nanofiltration membrane prepared by the interfacial polymerization method is generally low when the composite nanofiltration membrane realizes high rejection rate. Therefore, the preparation of nanofiltration membranes with high permeation flux and separation selectivity is one of the important research directions.
The zwitterionic compound has both anionic groups and cationic groups, and has strong hydration capability in aqueous solution, so that the separation membrane with the zwitterionic groups has good water permeability and anti-pollution performance. The Chinese patent 202110623073.6 discloses that the prepared zwitter-ion hollow fiber nano-particles are added into a piperazine water phase, and the composite nanofiltration membrane is prepared by interfacial polymerization with trimesoyl chloride. The zwitter-ion hollow nano particles are used as water molecule channels to improve water permeation flux. The Chinese patent 201110235694.3 discloses that polyamine and a zwitterionic compound are used as water phase monomers, polyacyl chloride is used as an organic phase monomer, and the polyamide nanofiltration membrane containing zwitterions is prepared by interfacial polymerization on the surface of a polysulfone membrane under an alkaline condition, has high water flux, shows high rejection rate (90-98%) on divalent salt ions, and has low rejection rate (less than 40%) on monovalent salt ions. The Chinese patent 202010264264.3 firstly carries out interfacial polymerization on the surface of an ultrafiltration membrane to prepare a polyamide separation layer, and then grafts a functional small molecular monomer with an amino or hydroxyl functional group by a secondary interfacial polymerization method to obtain a zwitterionic surface, thereby realizing the purposes of high flux and pollution resistance of the polyamide membrane. The Chinese patent 201910572400.2 firstly prepares zwitterions containing polyhydroxy through the reaction of triethanolamine and 2-bromoethyl sodium sulfonate, then soaks the nascent state polypiperazine amide nanofiltration membrane in the zwitterion water solution, and obtains the nanofiltration membrane with extremely strong hydrophilicity, high flux and rejection rate after thermal reaction.
Currently, zwitterionic surfaces are obtained mainly by adding zwitterionic compounds to aqueous solutions of interfacial polymerization or by modification of the separating layer after interfacial polymerization. The zwitterionic compound participates in the formation of the separation layer, so that the defect of the separation layer is easily caused, and the interception performance of the composite membrane is reduced; the amphoteric ion modification after the interfacial polymerization has no obvious effect on improving the permeation flux of the composite membrane, and the modification process is complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention solves the technical problems of low flux of the nanofiltration membrane and low separation selectivity of multivalent/monovalent inorganic salt.
The invention provides a preparation method of a composite nanofiltration membrane based on zwitterion regulation, which is characterized by comprising the following steps of:
a) dissolving a high molecular polymer for preparing a support membrane in an organic solvent, adding a pore-forming agent, preparing a membrane casting solution, and preparing an ultrafiltration/microfiltration support membrane by a phase inversion method, wherein the organic solvent is one or more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and N-vinylpyrrolidone, and the pore-forming agent is one of polyethylene glycol, polyvinylpyrrolidone and lithium chloride;
b) dissolving a polyphenol compound, a zwitterionic compound, an oxidant and a polyamine compound in a Tris buffer solution, and adjusting the pH value of the solution to 7.5-12 to prepare a deposition solution;
c) soaking the support film obtained in the step a) in the deposition solution obtained in the step b) for 1-24 hours, keeping the temperature of the deposition solution at 20-80 ℃, taking out the support film after deposition is finished, and placing the support film in deionized water for ultrasonic cleaning for 10 min;
d) fixing the support membrane obtained in the step c) in a polytetrafluoroethylene frame, pouring a diamine aqueous solution, standing for 1-20 min, pouring out the redundant solution, standing and drying the membrane at room temperature for 5-60 min, pouring a n-hexane solution of polyacyl chloride, standing for 0.5-20 min, and washing the surface of the membrane with the n-hexane solution to obtain a primary membrane;
e) drying the primary film obtained in the step d) in an oven at the temperature of 40-80 ℃ for 10-60 min.
Preferably, the polymer in the step a) is one or more than two of polysulfone, polyethersulfone, polyetheretherketone, sulfonated polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, hydrolyzed polyacrylonitrile and polypropylene, and the mass percentage of the polymer in the membrane casting solution is 5-20%; the thickness of the support membrane is 100-1000 μm, and the average pore diameter of the support membrane is 8-50 nm.
Preferably, the polyphenol compound in the step b) is one or more than two of caffeic acid, catechol, dopamine hydrochloride, 3, 4-dihydroxybenzoic acid, 2, 3-dihydroxybenzoic acid and 3, 4-dihydroxyphenylalanine; the zwitterion compound is one or more than two of 4-n-hexylbenzoylamino-propyl-dimethyl amino sulfobetaine, 2- (methacryloyloxy) ethyl-2- (trimethyl amino) ethyl phosphate, methacryloyl ethyl sulfobetaine, 2, 4-diaminobenzene sulfonic acid, 2, 5-diaminobenzene sulfonic acid and 3, 5-diaminobenzene sulfonic acid; the oxidant is one of ammonium persulfate and potassium persulfate; the polyamine compound is one or more of diethylenetriamine, ethylenediamine, triethylene tetramine, p-phenylenediamine and polyethyleneimine.
Preferably, the mass concentration of the polyphenol compound in the step b) is 1-10 g/L, the mass ratio of the zwitterionic compound to the polyphenol compound is 20: 1-1: 10, and the molar ratio of the polyphenol compound, the oxidant and the polyamine compound is 1-10: 0-1.
Preferably, in the step d), the diamine is one of piperazine and m-phenylenediamine, and the mass percent of the diamine is 0.1-5%; the polybasic acyl chloride is one of trimesoyl chloride, paraphthaloyl chloride and isophthaloyl chloride, and the mass percentage of the polybasic acyl chloride is 0.05-5%.
The invention provides a preparation method of a composite nanofiltration membrane based on zwitterion regulation and control, aiming at the problems of low flux of the nanofiltration membrane and low separation selectivity of multivalent/monovalent inorganic salt.
Compared with the prior art, the invention has the following advantages:
the preparation method of the composite nanofiltration membrane provided by the invention utilizes the mussel-like adhesion of the polyphenol compound to promote the stable existence of the zwitterionic compound on the surface of the support membrane; the strong hydrophilicity of the zwitterionic compound is utilized to optimize the interfacial polymerization reaction condition and the transmission channel of water molecules in the nanofiltration membrane, so that the flux of the nanofiltration membrane is improved; the charge action of the zwitter-ion group is utilized to enhance the attraction effect on inorganic salt ions, so that the selectivity of the nanofiltration membrane is improved.
The composite nanofiltration membrane obtained by the invention has wide application prospects in the aspects of dye removal, inorganic salt interception, multivalent/monovalent inorganic salt separation, antibiotic purification, drinking water purification, endocrine disrupter removal and the like.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The experimental reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The composite nanofiltration membrane prepared by the invention based on zwitterion regulation and control adopts a cross-flow filtering device to measure the separation and permeation performance, namely the flux and rejection rate of the membrane:
the flux (J) reflects the permeability of the membrane, J ═ V/(a · t). In the formulaV is the permeate volume (L) on the permeate side; a is the effective area (m) of the film2) (ii) a t is the permeation time (h).
The rejection (R) reflects the separation performance of the membrane, R ═ 1-Cp/Cf) X 100%. In the formula, CfAnd CpThe concentrations of solute components in the feed solution and permeate, respectively.
Specific examples of the present invention will be described below, but the present invention is not limited to the examples.
Example 1.
a) Dissolving polyacrylonitrile powder in N, N-dimethylformamide, adding polyethylene glycol, preparing 12% polyacrylonitrile membrane casting solution by mass, and preparing a flat plate support membrane with thickness of 250 μm and average pore diameter of 15nm by phase inversion method;
b) dissolving dopamine hydrochloride and methacryloyl ethyl sulfobetaine in a Tris buffer solution, wherein the mass concentration of the dopamine hydrochloride is 2g/L, the mass ratio of the methacryloyl ethyl sulfobetaine to the dopamine hydrochloride is 15: 1, and adjusting the pH value of the solution to 8.5 to prepare a deposition solution;
c) soaking the support film obtained in the step a) in the deposition solution obtained in the step b) for 8 hours, keeping the temperature of the deposition solution at 25 ℃, taking out the support film after deposition is finished, and placing the support film in deionized water for ultrasonic cleaning for 10 min;
d) fixing the support membrane obtained in the step c) in a polytetrafluoroethylene frame, pouring an aqueous solution with the mass percent of piperazine of 0.7%, standing for 5min, pouring out the redundant solution, standing and drying the membrane at room temperature for 20min, pouring an n-hexane solution with the mass percent of trimesoyl chloride of 0.2%, standing for 2min, and washing the surface of the membrane with the n-hexane solution to obtain a primary membrane;
e) drying the primary membrane obtained in the step d) in an oven at 60 ℃ for 20 min.
f) Testing the permeation and separation performance of the composite nanofiltration membrane obtained in the step e) by using a cross-flow filtering device at room temperature and 0.5MPa of operation pressure, wherein the pure water flux is 75 L.m-2·h-1For 1000mg/L Na2SO4、1000mg/L MgSO4、1000mg/L MgCl2And retention rates of 1000mg/L NaCl were respectively97%, 96%, 68% and 28%.
Example 2.
a) Dissolving polyacrylonitrile powder in N, N-dimethylformamide, adding polyethylene glycol, preparing 12% polyacrylonitrile membrane casting solution by mass, and preparing a flat plate support membrane with thickness of 250 μm and average pore diameter of 10nm by phase inversion method;
b) dissolving dopamine hydrochloride and 2, 4-diaminobenzene sulfonic acid in a Tris buffer solution, wherein the mass concentration of the dopamine hydrochloride is 2g/L, the mass ratio of the 2, 4-diaminobenzene sulfonic acid to the dopamine hydrochloride is 10: 1, and adjusting the pH value of the solution to 9 to prepare a deposition solution;
c) soaking the support film obtained in the step a) in the deposition solution obtained in the step b) for 12 hours, keeping the temperature of the deposition solution at 25 ℃, taking out the support film after deposition is finished, and placing the support film in deionized water for ultrasonic cleaning for 10 min;
d) fixing the support membrane obtained in the step c) in a polytetrafluoroethylene frame, pouring an aqueous solution with the mass percent of piperazine being 1%, standing for 5min, pouring out the redundant solution, standing and drying the membrane at room temperature for 20min, pouring an n-hexane solution with the mass percent of trimesoyl chloride being 0.5%, standing for 2min, and washing the surface of the membrane with the n-hexane solution to obtain a primary membrane;
e) drying the primary membrane obtained in the step d) in an oven at 60 ℃ for 20 min.
f) Testing the permeation and separation performance of the composite nanofiltration membrane obtained in the step e) by using a cross-flow filtering device at room temperature and 0.5MPa of operation pressure, wherein the pure water flux is 60 L.m-2·h-1For 1000mg/L Na2SO4、1000mg/L MgSO4、1000mg/L MgCl2And retention of 1000mg/L NaCl was 96%, 60% and 20%, respectively.
Example 3.
a) Dissolving polyether sulfone powder in N-methyl pyrrolidone, adding polyvinylpyrrolidone, preparing 12 mass percent of casting solution of polyether sulfone, and preparing a flat plate support membrane with the thickness of 500 mu m and the average pore diameter of 30nm by a phase inversion method;
b) dissolving caffeic acid, methacryloyl ethyl sulfobetaine, ammonium persulfate and ethylenediamine in a Tris buffer solution, wherein the mass concentration of the caffeic acid is 5g/L, the mass ratio of the methacryloyl ethyl sulfobetaine to the caffeic acid is 20: 1, the molar ratio of the caffeic acid, the ammonium persulfate and the ethylenediamine is 2: 1, and adjusting the pH value of the solution to 7.5 to prepare a deposition solution;
c) soaking the support film obtained in the step a) in the deposition solution obtained in the step b) for 4 hours, keeping the temperature of the deposition solution at 70 ℃, taking out the support film after the deposition is finished, and placing the support film in deionized water for ultrasonic cleaning for 10 min;
d) fixing the support membrane obtained in the step c) in a polytetrafluoroethylene frame, pouring a water solution with the mass percent of piperazine being 3%, standing for 3min, pouring out the redundant solution, standing and drying the membrane at room temperature for 30min, pouring a normal hexane solution with the mass percent of trimesoyl chloride being 1%, standing for 2min, and washing the surface of the membrane by using the normal hexane solution to obtain a primary membrane;
e) drying the primary membrane obtained in the step d) in an oven at 60 ℃ for 30 min.
f) Testing the permeation and separation performance of the composite nanofiltration membrane obtained in the step e) by using a cross-flow filtering device at room temperature and 0.5MPa of operation pressure, wherein the pure water flux is 110 L.m-2·h-1For 1000mg/L Na2SO4、1000mg/L MgSO4、1000mg/L MgCl2And retention of 1000mg/L NaCl was 80%, 78%, 45% and 8%, respectively.
Example 4.
a) Dissolving polyether sulfone powder in N-methyl pyrrolidone, adding polyvinylpyrrolidone, preparing a casting solution with the mass percent of polyether sulfone being 15%, and preparing a flat plate support membrane with the thickness of 300 mu m and the average pore diameter of 20nm by a phase inversion method;
b) dissolving caffeic acid, 2, 5-diaminobenzene sulfonic acid, potassium persulfate and polyethyleneimine in a Tris buffer solution, wherein the mass concentration of the caffeic acid is 4g/L, the mass ratio of the 2, 5-diaminobenzene sulfonic acid to the caffeic acid is 15: 1, the molar ratio of the caffeic acid, the potassium persulfate and the polyethyleneimine is 5: 1, and adjusting the pH value of the solution to 8 to prepare a deposition solution;
c) soaking the support film obtained in the step a) in the deposition solution obtained in the step b) for 2 hours, keeping the temperature of the deposition solution at 65 ℃, taking out the support film after deposition is finished, and placing the support film in deionized water for ultrasonic cleaning for 10 min;
d) fixing the support membrane obtained in the step c) in a polytetrafluoroethylene frame, pouring an aqueous solution with the mass percent of piperazine being 5%, standing for 4min, pouring out the redundant solution, standing and drying the membrane at room temperature for 30min, pouring an n-hexane solution with the mass percent of trimesoyl chloride being 3%, standing for 2min, and washing the surface of the membrane with the n-hexane solution to obtain a primary membrane;
e) drying the primary membrane obtained in the step d) in an oven at 60 ℃ for 30 min.
f) Testing the permeation and separation performance of the composite nanofiltration membrane obtained in the step e) by using a cross-flow filtering device at room temperature and 0.5MPa of operation pressure, wherein the pure water flux is 94 L.m-2·h-1For 1000mg/L Na2SO4、1000mg/L MgSO4、1000mg/L MgCl2And retention of 1000mg/L NaCl was 88%, 87%, 59%, and 10%, respectively.
Claims (10)
1. A preparation method of a composite nanofiltration membrane based on zwitterion regulation is characterized by comprising the following steps:
a) dissolving a high molecular polymer for preparing a support membrane in an organic solvent, adding a pore-forming agent, preparing a membrane casting solution, and preparing an ultrafiltration/microfiltration support membrane by a phase inversion method, wherein the organic solvent is one or more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and N-vinylpyrrolidone, and the pore-forming agent is one of polyethylene glycol, polyvinylpyrrolidone and lithium chloride;
b) dissolving a polyphenol compound, a zwitterionic compound, an oxidant and a polyamine compound in a Tris buffer solution, and adjusting the pH value of the solution to 7.5-12 to prepare a deposition solution;
c) soaking the support film obtained in the step a) in the deposition solution obtained in the step b) for 1-24 hours, keeping the temperature of the deposition solution at 20-80 ℃, taking out the support film after deposition is finished, and placing the support film in deionized water for ultrasonic cleaning for 10 min;
d) fixing the support membrane obtained in the step c) in a polytetrafluoroethylene frame, pouring a diamine aqueous solution, standing for 1-20 min, pouring out the redundant solution, standing and drying the membrane at room temperature for 5-60 min, pouring a n-hexane solution of polyacyl chloride, standing for 0.5-20 min, and washing the surface of the membrane with the n-hexane solution to obtain a primary membrane;
e) drying the primary film obtained in the step d) in an oven at the temperature of 40-80 ℃ for 10-60 min.
2. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step a), the high molecular polymer is one or more than two of polysulfone, polyethersulfone, polyether ether ketone, sulfonated polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, hydrolyzed polyacrylonitrile and polypropylene, and the mass percentage of the high molecular polymer in the membrane casting solution is 5-20%.
3. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step a), the thickness of the support membrane is 100-1000 μm, and the average pore diameter of the support membrane is 8-50 nm.
4. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step b), the polyphenol compound is one or more than two of caffeic acid, catechol, dopamine hydrochloride, 3, 4-dihydroxybenzoic acid, 2, 3-dihydroxybenzoic acid and 3, 4-dihydroxyphenylalanine.
5. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step b), the zwitterionic compound is one or more than two of 4-n-hexylbenzoylamino-propyl-dimethylamino sulfobetaine, 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate, methacryloylethyl sulfobetaine, 2, 4-diaminobenzene sulfonic acid, 2, 5-diaminobenzene sulfonic acid and 3, 5-diaminobenzene sulfonic acid.
6. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step b), the oxidant is one of ammonium persulfate and potassium persulfate.
7. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step b), the polyamine compound is one or more than two of diethylenetriamine, ethylenediamine, triethylene tetramine, p-phenylenediamine and polyethyleneimine.
8. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step b), the mass concentration of the polyphenol compound is 1-10 g/L, the mass ratio of the zwitterionic compound to the polyphenol compound is 20: 1-1: 10, and the molar ratio of the polyphenol compound, the oxidant and the polyamine compound is 1-10: 0-1.
9. The preparation method of the composite nanofiltration membrane based on zwitterion regulation and control, according to claim 1, characterized in that: in the step d), diamine is one of piperazine and m-phenylenediamine, and the mass percent of the diamine is 0.1-5%; the polybasic acyl chloride is one of trimesoyl chloride, paraphthaloyl chloride and isophthaloyl chloride, and the mass percentage of the polybasic acyl chloride is 0.05-5%.
10. The composite nanofiltration membrane obtained by the preparation method of claim 1 is applied to dye removal, inorganic salt interception, multivalent/monovalent inorganic salt separation, antibiotic purification, drinking water purification and endocrine disrupter removal.
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