CN117771943A - Charged positive nanofiltration composite membrane and preparation method and application thereof - Google Patents
Charged positive nanofiltration composite membrane and preparation method and application thereof Download PDFInfo
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- CN117771943A CN117771943A CN202410036004.9A CN202410036004A CN117771943A CN 117771943 A CN117771943 A CN 117771943A CN 202410036004 A CN202410036004 A CN 202410036004A CN 117771943 A CN117771943 A CN 117771943A
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- 239000012528 membrane Substances 0.000 title claims abstract description 95
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000008346 aqueous phase Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000012074 organic phase Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000768 polyamine Polymers 0.000 claims abstract description 16
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 5
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 4
- 239000000412 dendrimer Substances 0.000 claims description 4
- 229920000736 dendritic polymer Polymers 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000008233 hard water Substances 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 claims description 3
- GHITVUOBZBZMND-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=CC(CBr)=C1 GHITVUOBZBZMND-UHFFFAOYSA-N 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 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229920005597 polymer membrane Polymers 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000981 basic dye Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- 230000014759 maintenance of location Effects 0.000 description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- MWWSFMDVAYGXBV-RUELKSSGSA-N Doxorubicin hydrochloride Chemical compound Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 MWWSFMDVAYGXBV-RUELKSSGSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229960002918 doxorubicin hydrochloride Drugs 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- LLWJPGAKXJBKKA-UHFFFAOYSA-N victoria blue B Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C(C=C1)C2=CC=CC=C2C1=[NH+]C1=CC=CC=C1 LLWJPGAKXJBKKA-UHFFFAOYSA-N 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 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
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of lithium-magnesium separation, in particular to a positively charged nanofiltration composite membrane and a preparation method and application thereof, and the preparation method comprises the following steps: preparing aqueous phase solution containing polyamine monomer, acid acceptor, surfactant and residual water; preparing an organic phase solution containing benzyl bromide monomers and the balance of organic solvent; after the porous support film is contacted with the aqueous phase solution, pouring out the redundant aqueous phase solution, and removing residual liquid drops on the surface to obtain the support film adsorbed with polyamine monomers; pouring the organic phase solution on the surface of a support film adsorbed with polyamine monomers, and obtaining a nascent nanofiltration film after interfacial polymerization reaction; and (3) placing the obtained nascent nanofiltration membrane in a drying oven for heat treatment to obtain the positively charged nanofiltration composite membrane. The invention adopts the positively charged nanofiltration composite membrane and the preparation method and the application thereof, and solves the problems of low permeation flux and low separation efficiency of the traditional positively charged nanofiltration composite membrane material.
Description
Technical Field
The invention relates to the technical field of lithium-magnesium separation, in particular to a positively charged nanofiltration composite membrane and a preparation method and application thereof.
Background
The nanofiltration membrane is a pressure driven membrane, the pore diameter is generally about 0.5-2 nm, and the molecular weight cut-off is 200-2000 Da. The separation mechanism of the nanofiltration membrane on monovalent/divalent cations is mainly based on steric hindrance effect, electrostatic repulsion effect, dielectric effect and transmission energy barrier. Under the action of electrostatic repulsion effect, the positively charged nanofiltration composite membrane can effectively intercept positively charged organic matters and divalent and multivalent cations, thereby playing an important role in positively charged organic pollutant removal, lithium-magnesium separation, hard water softening, heavy metal wastewater treatment, alkaline dye separation, drug concentration, antibiotic extraction and the like.
The preparation method of the charged nanofiltration composite membrane mainly comprises an interfacial polymerization method and a surface grafting method. The polyethyleneimine has the advantages of high reactivity and good hydrophilicity, and contains a large number of primary, secondary and tertiary amine groups in the molecular structure. The polyquaternary ammonium salt is a cationic polymer and has the advantage of good water solubility. Therefore, a plurality of researchers prepare the positively charged nanofiltration composite membrane by interfacial polymerization reaction of polyethylene imine and quaternary ammonium salt aqueous phase monomers and polybasic acyl chloride organic phase monomers, and the positively charged nanofiltration composite membrane can be better applied to the fields of positively charged organic pollutant removal, lithium-magnesium separation, heavy metal pollutant removal and the like. In addition, some researchers graft polyethyleneimine and quaternary ammonium molecules on the surface of a nanofiltration membrane to obtain positively charged surface properties.
However, because the polyethylene imine and quaternary ammonium salt monomers have stronger activity, the polyamide structure formed by the polyethylene imine and quaternary ammonium salt monomers and the high-activity polyacyl chloride monomers has high crosslinking degree but limited positive charge density, and the prepared positive charge nanofiltration composite membrane generally has the problems of low flux and low selectivity. Therefore, the development of the high-performance and easy-to-prepare strong-charge positive nanofiltration composite membrane has important practical significance.
Disclosure of Invention
The invention aims to provide a positively charged nanofiltration composite membrane, a preparation method and application thereof, and solves the problems of low permeation flux and low separation efficiency of the traditional positively charged nanofiltration composite membrane material.
In order to achieve the above purpose, the invention provides a preparation method of a charged positive nanofiltration composite membrane, which comprises the following steps:
s1, preparing aqueous phase solution containing polyamine monomer with mass concentration of 0.1-6%, acid receiver with mass concentration of 0.1-2%, surfactant with mass concentration of 0.1-2% and the balance water; the polyamine monomer comprises one or more of polyetheramine, polyethyleneimine, polyamide-amine dendritic polymer, polyethylenepolyamine, polypropyleneimine and m-phenylenediamine;
s2, preparing an organic phase solution containing 0.1-6% of benzyl bromide monomer and the balance of organic solvent;
s3, after the porous support film is contacted with the aqueous phase solution, pouring out the redundant aqueous phase solution, and removing residual liquid drops on the surface to obtain the support film adsorbed with the polyamine monomer;
s4, pouring the organic phase solution on the surface of the support membrane adsorbed with the polyamine monomer, and performing interfacial polymerization reaction to obtain a nascent nanofiltration membrane;
s5, placing the nascent state nanofiltration membrane obtained in the S4 in a drying oven for heat treatment to obtain the positively charged nanofiltration composite membrane.
More preferably, the mass concentration of the polyamine monomer is 1 to 3%.
Preferably, the acid acceptor in S1 is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide and potassium carbonate.
More preferably, the acid acceptor is sodium carbonate and sodium bicarbonate.
Preferably, the surfactant in S1 is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween 20 and hexadecyl trimethyl ammonium bromide.
Preferably, the organic solvent in S2 includes one or more of n-heptane, n-hexane, ethyl acetate, toluene, and mesitylene.
Preferably, the benzyl bromide monomer in S2 comprises one or more of 1, 4-di (bromomethyl) benzene, 1,3, 5-tri (bromomethyl) benzene, 1,3, 5-tribromobenzene and 1, 4-dibromobenzene.
More preferably, the mass concentration of the benzyl bromide monomer is 0.5 to 2%.
Preferably, the porous support membrane in S3 is a polymer membrane or an inorganic porous membrane with a molecular weight cut-off of 5-50 kDa.
More preferably, the porous support membrane is one of polyimide, polytetrafluoroethylene, polyacrylonitrile, polypropylene, polyethylene, polysulfone, polyethersulfone, polyvinylidene fluoride, alumina porous membrane.
Preferably, the contact operation in S3 is soaking or dipping, the contact time is 0.5-30 minutes, and the contact temperature is 10-60 ℃.
Preferably, the interfacial polymerization reaction time in S4 is 0.5-30 minutes, and the reaction temperature is 10-60 ℃.
Preferably, the heat treatment time in S5 is 5-60 minutes, and the heat treatment temperature is 50-100 ℃.
A positively charged nanofiltration composite membrane prepared by a preparation method of the positively charged nanofiltration composite membrane.
The application of the positively charged nanofiltration composite membrane is applied to positively charged organic pollutant removal, lithium-magnesium separation, hard water softening, heavy metal wastewater treatment, alkaline dye separation, drug concentration and antibiotic extraction.
The reaction mechanism of the invention: the amine monomer used in the invention is of a chain structure or a dendritic structure, and nucleophilic substitution reaction is carried out between the amino group of the polyamine monomer and the bromomethyl group of the benzyl bromide monomer to form a compact layer of polyamine connected by C-N single bond. According to the activity and density of the amino groups contained in the chain structure or the dendritic structure, the compactness of the polyamine layer can be effectively regulated. The charged nanofiltration composite membrane with a compact structure can be used for separating salt, such as lithium and magnesium separation. The positively charged nanofiltration composite membrane with a loose structure can be used for separating positively charged small molecules, such as medicines or dyes. In the reaction process, the added acid acceptor is used for adjusting the pH value of the reaction liquid and promoting the polymerization reaction between monomers so that the monomers can be rapidly formed into a film at the interface.
The invention has the beneficial effects that:
(1) The separation layer of the charged nanofiltration composite membrane is stable and firm, and has good long-term operation stability.
(2) The positively charged nanofiltration composite membrane has high surface positive charge density and excellent retention rate on divalent and multivalent cations and positively charged small molecules, such as magnesium ions, heavy metal ions, victoria blue B, doxorubicin hydrochloride and the like.
(3) The positively charged nanofiltration composite membrane can be applied to the fields of positively charged organic pollutant removal, lithium-magnesium separation, hard water softening, heavy metal wastewater treatment, alkaline dye separation, drug concentration, antibiotic extraction and the like.
(4) The preparation method of the charged nanofiltration composite membrane has the advantages of simple process, low monomer concentration, mild preparation conditions, wide application range, easy amplification and popularization and easy realization of industrial production.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a surface scanning electron microscope image of a support film in example 1 of the present invention;
FIG. 2 is a surface scanning electron microscope image of the positively charged nanofiltration composite membrane of example 1 of the present invention;
FIG. 3 is a cross-sectional scanning electron microscope image of the positively charged nanofiltration composite membrane of example 1 of the present invention;
FIG. 4 shows the Zeta potential of the surface of the charged nanofiltration composite membrane and the support membrane at different pH values in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to examples. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The above-mentioned features of the invention or the features mentioned in the specific examples can be combined in any desired manner, and these specific examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.
The flux detection method of the charged nanofiltration composite membrane comprises the following steps:
the membrane permeation flux and salt rejection rate of the membrane to water are tested by adopting a membrane permeation selective performance test system, wherein the test system comprises a pump, a membrane tank, a pipeline, a regulating valve, a pressure detector and a flow detector, the test pressure is 3bar, and the test temperature is 25+/-0.5 ℃. The retention performance of the charged positive nanofiltration composite membrane on divalent salt and monovalent salt was tested with magnesium chloride and lithium chloride (sodium chloride). Salt concentration for single salt rejection was measured to be 0.1 g.L -1 Salt concentration of 0.2 g.L for testing the separation performance of mixed salt -1 . Ion concentration is detected using inductively coupled plasma emission spectroscopy. The interception performance of the charged positive nanofiltration composite membrane on small molecules is tested by taking Victoria blue B and doxorubicin hydrochloride as solute molecules.
The calculation formula of the pure water permeation flux is as follows:
J＝V/(A·△t·P)
wherein J is the pure water permeation flux (L.m -2 ·h -1 ) V is the water volume (L) passing through the membrane, A is the effective membrane area (m 2 ) Δt is the permeation time (h), P is the operating pressure (bar).
The formula for the retention rate R is as follows:
R＝(1-C p /C f )*100％
wherein C is p Is the solute concentration (g.L) -1 )，C f Is the concentration (g.L) of the solute in the raw material liquid -1 )。
Monovalent ion/divalent ion Selectivity S 1,2 The calculation formula of (2) is as follows:
wherein C is 1,P And C 2,P The concentration of ion 1 and ion 2 in the permeate (g.L -1 )；C 1,f And C 2,f The concentration of ion 1 and ion 2 (g.L) -1 )。
Example 1
An aqueous phase solution containing 2% of polyetheramine, 3% of polyethylene polyamine, 1% of sodium hydrogencarbonate and 0.5% of sodium dodecylbenzenesulfonate and the balance of water was prepared as an aqueous phase solution. An organic phase solution containing 1%1, 4-bis (bromomethyl) benzene and the balance n-heptane was prepared. And placing the aqueous phase solution on the surface of a polyethersulfone supporting membrane, adsorbing for 5 minutes, pouring out the excessive aqueous phase solution, and removing residual liquid drops on the surface. Thereafter, the organic phase solution was placed on the membrane surface, subjected to interfacial polymerization for 10 minutes, the excess organic phase solution was removed, and unreacted monomers were washed with n-hexane. And (3) placing the nascent nanofiltration membrane in a drying oven at 85 ℃ for heat treatment for 10 minutes to obtain the positively charged nanofiltration composite membrane.
Through test, the Zeta potential of the charged nanofiltration composite membrane under the condition of pH 7.0 is +18mV, and the pure water permeation flux is 6.2 L.m -2 ·h -1 The magnesium chloride retention rate is 94%, the lithium chloride retention rate is 32%, and the sodium chloride retention rate is 30%. The lithium magnesium and sodium magnesium separation factor of the mixed salt solution test was about 12.
Example 2
An aqueous phase solution containing 1% polyethylenimine (molecular weight of 70000 Da), 1% polyamide-amine dendrimer, 1% sodium bicarbonate and 1% sodium dodecyl sulfate and the balance water was prepared as an aqueous phase solution. An organic phase solution containing 2% of 1,3, 5-tribromobenzene and the balance of n-hexane was prepared. And placing the aqueous phase solution on the surface of a polyethersulfone supporting membrane, adsorbing for 10 minutes, pouring out the excessive aqueous phase solution, and removing residual liquid drops on the surface. Thereafter, the organic phase solution was placed on the membrane surface, subjected to interfacial polymerization for 5 minutes, the excess organic phase solution was removed, and the unreacted monomers were rinsed off with n-heptane. And (3) placing the nascent nanofiltration membrane in a drying oven at 90 ℃ for heat treatment for 5 minutes to obtain the positively charged nanofiltration composite membrane.
Through test, the Zeta potential of the charged nanofiltration composite membrane under the condition of pH 7.0 is +22mV, and the pure water permeation flux is 5.6L.m -2 ·h -1 The magnesium chloride retention rate is 95%, the lithium chloride retention rate is 30%, and the sodium chloride retention rate is 30%. Mixed salt solutionThe lithium magnesium and sodium magnesium separation factor tested was about 13.
Example 3
An aqueous phase solution containing 2% of a polyamide-amine dendrimer, 1% of a polyether amine, 1% of sodium hydrogencarbonate and 1% of sodium lauryl sulfate and the balance of water was prepared as an aqueous phase solution. An organic phase solution containing 0.5%1,3, 5-tris (bromomethyl) benzene and the balance n-heptane was prepared. And placing the aqueous phase solution on the surface of a polyacrylonitrile support film, adsorbing for 10 minutes, pouring out the excessive aqueous phase solution, and removing residual liquid drops on the surface. Thereafter, the organic phase solution was placed on the membrane surface, subjected to interfacial polymerization for 10 minutes, the excess organic phase solution was removed, and the unreacted monomers were rinsed with n-heptane. And (3) placing the nascent nanofiltration membrane in a drying oven at 90 ℃ for heat treatment for 5 minutes to obtain the positively charged nanofiltration composite membrane.
Through test, the Zeta potential of the charged positive nanofiltration composite membrane under the condition of pH 7.0 is +20mV, and the pure water permeation flux is 10L.m -2 ·h -1 The retention rate of magnesium chloride is 90%, the retention rate of lithium chloride is 21%, the retention rate of Victoria blue B is 99%, and the retention rate of doxorubicin hydrochloride is 99%.
Example 4
An aqueous phase solution containing 2% of polypropylene imine, 1% of m-phenylenediamine, 0.5% of potassium carbonate, 1% of cetyl trimethylammonium bromide and the balance of water was prepared as an aqueous phase solution. An organic phase solution containing 1%1, 4-bis (bromomethyl) benzene and the balance n-heptane was prepared. And placing the aqueous phase solution on the surface of the polysulfone support membrane, adsorbing for 10 minutes, pouring out the excessive aqueous phase solution, and removing residual liquid drops on the surface. Thereafter, the organic phase solution was placed on the membrane surface, subjected to interfacial polymerization for 20 minutes, the excess organic phase solution was removed, and the unreacted monomers were rinsed with n-heptane. And (3) placing the nascent nanofiltration membrane in a drying oven at 80 ℃ for heat treatment for 10 minutes to obtain the positively charged nanofiltration composite membrane.
Through test, the Zeta potential of the charged positive nanofiltration composite membrane under the condition of pH 7.0 is +15mV, and the pure water permeation flux is 18 L.m -2 ·h -1 The retention rate of magnesium chloride is 20%, the retention rate of lithium chloride is 5%, the retention rate of Victoria blue B is 90%, and the retention rate of doxorubicin hydrochloride is 92%.
The positively charged nanofiltration composite membrane obtained in example 1 was subjected to long-term operation stability test, and after 50 hours of continuous separation test, the retention rate of the membrane to magnesium chloride was basically unchanged, and the water permeation flux was reduced by about 5%, which indicates that the prepared positively charged nanofiltration composite membrane has good long-term operation stability.
The surface morphology and the cross-section morphology of the positively charged nanofiltration composite membrane obtained in example 1 were observed by using a scanning electron microscope. Fig. 1 is a surface scanning electron microscope image of the support film in example 1 of the present invention, and fig. 2 is a surface scanning electron microscope image of the positively charged nanofiltration composite film in example 1 of the present invention, as shown in fig. 2, the surface of the positively charged nanofiltration composite film prepared is smooth, dense and defect-free. FIG. 3 is a cross-sectional scanning electron microscope image of the positively charged nanofiltration composite membrane of example 1 according to the present invention, wherein the separation layer thickness of the positively charged nanofiltration composite membrane is about 150nm as shown in FIG. 3.
FIG. 4 is a schematic diagram of the Zeta potential of the positively charged nanofiltration composite membrane and the support membrane in example 1 of the present invention at different pH values, and as shown in FIG. 4, the positively charged nanofiltration membrane has a surface characteristic of strong positive charge in the pH range of 5.0-8.0, and the Zeta potential reaches +20mV.
Therefore, the positively charged nanofiltration composite membrane provided by the invention has the advantages of simple preparation method, mild conditions, wide application range, easiness in amplification and industrial production, strong separation layer firmness of the prepared positively charged nanofiltration composite membrane and good long-term operation stability.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (8)
1. The preparation method of the positively charged nanofiltration composite membrane is characterized by comprising the following steps of:
s1, preparing aqueous phase solution containing polyamine monomer with mass concentration of 0.1-6%, acid receiver with mass concentration of 0.1-2%, surfactant with mass concentration of 0.1-2% and the balance water; the polyamine monomer comprises one or more of polyetheramine, polyethyleneimine, polyamide-amine dendritic polymer, polyethylenepolyamine, polypropyleneimine and m-phenylenediamine;
s2, preparing an organic phase solution containing 0.1-6% of benzyl bromide monomer and the balance of organic solvent;
s3, after the porous support film is contacted with the aqueous phase solution, pouring out the redundant aqueous phase solution, and removing residual liquid drops on the surface to obtain the support film adsorbed with the polyamine monomer;
s4, pouring the organic phase solution on the surface of the support membrane adsorbed with the polyamine monomer, and performing interfacial polymerization reaction to obtain a nascent nanofiltration membrane;
s5, placing the nascent state nanofiltration membrane obtained in the S4 in a drying oven for heat treatment to obtain the positively charged nanofiltration composite membrane.
2. The method for preparing the positively charged nanofiltration composite membrane according to claim 1, wherein the method comprises the following steps: the acid acceptor in S1 is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide and potassium carbonate.
3. The method for preparing the positively charged nanofiltration composite membrane according to claim 1, wherein the method comprises the following steps: the surfactant in S1 is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, tween 20 and hexadecyl trimethyl ammonium bromide.
4. The method for preparing the positively charged nanofiltration composite membrane according to claim 1, wherein the method comprises the following steps: the organic solvent in S2 comprises one or more of n-heptane, n-hexane, ethyl acetate, toluene and mesitylene.
5. The method for preparing the positively charged nanofiltration composite membrane according to claim 1, wherein the method comprises the following steps: the benzyl bromide monomer in S2 comprises one or more of 1, 4-di (bromomethyl) benzene, 1,3, 5-tri (bromomethyl) benzene, 1,3, 5-tribromobenzene and 1, 4-dibromobenzene.
6. The method for preparing the positively charged nanofiltration composite membrane according to claim 1, wherein the method comprises the following steps: the porous support membrane in S3 is a polymer membrane or an inorganic porous membrane with the molecular weight cutoff of 5-50 kDa.
7. A positively charged nanofiltration composite membrane produced by the process of any one of claims 1 to 6.
8. Use of a positively charged nanofiltration composite membrane as claimed in claim 7, wherein: the method is applied to positively charged organic pollutant removal, lithium-magnesium separation, hard water softening, heavy metal wastewater treatment, basic dye separation, drug concentration and antibiotic extraction.
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| US20140251897A1 (en) * | 2011-10-18 | 2014-09-11 | Imperial Innovations Limited | Membranes for separation |
| CN113083032A (en) * | 2021-04-26 | 2021-07-09 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
| CN115364684A (en) * | 2022-10-25 | 2022-11-22 | 天津大学 | High-flux positively-charged nanofiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140251897A1 (en) * | 2011-10-18 | 2014-09-11 | Imperial Innovations Limited | Membranes for separation |
| CN113083032A (en) * | 2021-04-26 | 2021-07-09 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
| CN115364684A (en) * | 2022-10-25 | 2022-11-22 | 天津大学 | High-flux positively-charged nanofiltration membrane and preparation method thereof |
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