CN113559728A - Acid-resistant composite nanofiltration membrane and preparation method thereof - Google Patents
Acid-resistant composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN113559728A CN113559728A CN202110832858.4A CN202110832858A CN113559728A CN 113559728 A CN113559728 A CN 113559728A CN 202110832858 A CN202110832858 A CN 202110832858A CN 113559728 A CN113559728 A CN 113559728A
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- 239000012528 membrane Substances 0.000 title claims abstract description 178
- 239000002253 acid Substances 0.000 title claims abstract description 105
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000012074 organic phase Substances 0.000 claims abstract description 32
- 229920000768 polyamine Polymers 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 56
- 239000008346 aqueous phase Substances 0.000 claims description 32
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- ZBJSGOMTEOPTBH-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC(S(Cl)(=O)=O)=CC2=CC(S(=O)(=O)Cl)=CC=C21 ZBJSGOMTEOPTBH-UHFFFAOYSA-N 0.000 claims description 19
- 229920002492 poly(sulfone) Polymers 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002250 absorbent Substances 0.000 claims description 12
- 230000002745 absorbent Effects 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012971 dimethylpiperazine Substances 0.000 claims description 5
- 150000007519 polyprotic acids Polymers 0.000 claims description 5
- GUXHBMASAHGULD-SEYHBJAFSA-N (4s,4as,5as,6s,12ar)-7-chloro-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-3,12-dioxo-4a,5,5a,6-tetrahydro-4h-tetracene-2-carboxamide Chemical group C1([C@H]2O)=C(Cl)C=CC(O)=C1C(O)=C1[C@@H]2C[C@H]2[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]2(O)C1=O GUXHBMASAHGULD-SEYHBJAFSA-N 0.000 claims description 4
- UIMAOHVEKLXJDO-UHFFFAOYSA-N (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;triethylazanium Chemical compound CCN(CC)CC.C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C UIMAOHVEKLXJDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 3
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 3
- VPLHHUICIOEESV-UHFFFAOYSA-N naphthalene-2,6-disulfonyl chloride Chemical compound C1=C(S(Cl)(=O)=O)C=CC2=CC(S(=O)(=O)Cl)=CC=C21 VPLHHUICIOEESV-UHFFFAOYSA-N 0.000 claims description 3
- IHZVARNFIMXWFZ-UHFFFAOYSA-N piperazine-2,3-diamine Chemical compound N1C(C(NCC1)N)N IHZVARNFIMXWFZ-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- PVJZBZSCGJAWNG-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonyl chloride Chemical compound CC1=CC(C)=C(S(Cl)(=O)=O)C(C)=C1 PVJZBZSCGJAWNG-UHFFFAOYSA-N 0.000 claims description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 2
- PIPWSBOFSUJCCO-UHFFFAOYSA-N 2,2-dimethylpiperazine Chemical compound CC1(C)CNCCN1 PIPWSBOFSUJCCO-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 61
- 230000004907 flux Effects 0.000 abstract description 30
- 239000002346 layers by function Substances 0.000 abstract description 25
- 150000001263 acyl chlorides Chemical class 0.000 abstract description 18
- 238000011033 desalting Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 44
- 238000012695 Interfacial polymerization Methods 0.000 description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- 238000004132 cross linking Methods 0.000 description 12
- 238000010612 desalination reaction Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- GNIZQCLFRCBEGE-UHFFFAOYSA-N 3-phenylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(Cl)=O GNIZQCLFRCBEGE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004063 acid-resistant material Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an acid-resistant composite nanofiltration membrane and a preparation method thereof. Wherein the preparation method comprises the following steps: (1) contacting the porous support layer with an aqueous solution containing a polyamine and drying; (2) contacting the porous support layer obtained in the step (1) with an organic phase solution containing sulfonyl chloride and a polybasic acyl chloride monomer, and drying; (3) and (3) carrying out heat treatment on the porous supporting layer obtained in the step (2) so as to obtain the acid-resistant composite nanofiltration membrane. The method is simple in process, can effectively solve the problems of looseness and rough surface of a functional layer of the polysulfonamide nanofiltration membrane, improves the desalting performance and water flux of the polysulfonamide nanofiltration membrane, ensures the acid resistance of the polysulfonamide nanofiltration membrane, and simultaneously ensures that the performance stability of the prepared acid-resistant composite nanofiltration membrane is good.
Description
Technical Field
The invention belongs to the field of nanofiltration membranes, and particularly relates to an acid-resistant composite nanofiltration membrane and a preparation method thereof.
Background
In the field of water treatment, nanofiltration is a pressure-driven membrane separation process between ultrafiltration and reverse osmosis, the membrane aperture is in a nanometer level, a better removal effect is achieved on multivalent ions and organic matters with the molecular weight of 200-1000, most of nanofiltration membranes are positively charged under an acidic condition and negatively charged under a neutral or alkaline condition, and the surface charges endow the nanofiltration membranes with unique separation advantages. The nanofiltration separation technology is used as a new branch in the membrane technology, and due to the unique aperture and charge performance ratio of the nanofiltration membrane, the utility of the nanofiltration membrane in modern chemical production is increased day by day, so that the nanofiltration separation technology is widely applied to a plurality of fields such as water treatment, electronics, chemical industry, medicines, foods and the like. In the actual chemical production process, the strongly acidic solution to be treated is common in the industrial field.
The surface functional layer of the mainstream composite nanofiltration membrane in the market at present is still a polypiperazine amide cross-linked network structure formed by interfacial polymerization reaction based on 1,3, 5-benzene tricarboxychloride and piperazine, and the tolerance range of pH is generally 2-10. When strong-acid feed liquid is treated, particularly during long-term treatment, amide bonds in a functional layer on the surface of the membrane are protonated, so that the hydrolytic breakage of the amide bonds and the degradation of the microstructure of the membrane are caused, the high degradation of the membrane is caused, the mechanical strength is greatly attenuated, the separation performance of the membrane is reduced, the application of the polypiperazine amide nanofiltration membrane in an acid environment is restricted, and the economic cost is increased by frequently replacing the separation membrane. Therefore, the development of a novel acid-resistant nanofiltration membrane with excellent performance and good separation performance has far-reaching significance for treating strong-acid feed liquid.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
The present invention has been completed based on the following findings of the inventors:
at present, researches on the improvement of the acid resistance stability are mainly carried out from two aspects of selecting membrane materials and modifying the surface of the membrane. The stability of the membrane material largely determines the stability of the separation membrane, namely, the selection of the membrane material is the primary method for improving the acid stability of the nanofiltration membrane. The acid-resistant nanofiltration membrane is required to have stable chemical bonds and certain hydrolysis resistance under an acidic condition. The benzene ring, ether bond, sulfone group, heterocycle and the like have better chemical inertness, and the high-molecular compound formed by the chemical bonds always shows strong conjugation effect, so the acid-resistant film can be used as a material selection object. In addition, the polymer chain must have a certain polar group (chemical bond) to ensure that the prepared membrane has good permeability and separation selectivity.
The polysulfonamide is a high-molecular material similar to polyamide, has strong conjugation in the whole molecule, is difficult to protonate oxygen in a sulfonamide bond under an acidic condition, has excellent hydrolysis resistance, and can improve the acid resistance of the film. At present, the acid-resistant nanofiltration membrane is prepared by an interfacial polymerization reaction of multipurpose sulfonyl chloride monomers and polyamine, but because the synthetic activity of polysulfonamide is lower than that of polyamide, the functional layer of the prepared polysulfonamide nanofiltration membrane is loose and has rough surface, and the desalting performance and the water flux cannot reach the level of the polypiperazine amide nanofiltration membrane; if the polysulfonamide nanofiltration membrane is generated on the porous supporting layer through the interfacial polymerization reaction of heterocyclic polyamine and polynary naphthaloyl chloride, although the acid resistance is excellent, the rejection rate of the membrane is not high and is 70-85%. In addition, although the polyamine aqueous solution and the sulfonyl chloride organic phase solution are alternately assembled layer by layer on the surface of the porous support layer and the nanofiltration membrane is prepared by heat treatment, the desalination performance and the acid resistance of the membrane can be improved, and the roughness is reduced to a certain extent, but the flux of the membrane is not high.
In view of the above, an object of the present invention is to provide a method for preparing an acid-resistant composite nanofiltration membrane, which has a simple process, can effectively solve the problems of looseness and rough surface of a functional layer of a polysulfonamide nanofiltration membrane, and can improve the desalination performance and water flux of the polysulfonamide nanofiltration membrane.
In one aspect of the invention, the invention provides a method for preparing an acid-resistant composite nanofiltration membrane. According to an embodiment of the invention, the method comprises:
(1) contacting the porous support layer with an aqueous solution containing a polyamine and drying;
(2) contacting the porous support layer obtained in the step (1) with an organic phase solution containing sulfonyl chloride and a polybasic acyl chloride monomer, and drying;
(3) and (3) carrying out heat treatment on the porous supporting layer obtained in the step (2) so as to obtain the acid-resistant composite nanofiltration membrane.
According to the method for preparing the acid-resistant composite nanofiltration membrane, the inventor finds that an acid-resistant material sulfonyl chloride can be used as a reaction monomer in an organic phase solution to prepare the polysulfonamide nanofiltration membrane and improve the acid resistance of the polysulfonamide nanofiltration membrane, and meanwhile, the crosslinking degree in interfacial polymerization can be improved by adding polyacyl chloride in the organic phase solution blending, so that the prepared functional layer is compact, the roughness is obviously improved, and the desalting performance and the water flux performance of the nanofiltration membrane can be further improved. Therefore, the preparation method is simple in process, the acid resistance of the nanofiltration membrane is improved, the crosslinking degree of interfacial polymerization reaction can be improved, the prepared functional layer is compact, the roughness is obviously improved, the membrane performance is still stable after one month of acid waste liquid treatment, and the preparation method has a good application prospect in acid industrial wastewater treatment.
According to an embodiment of the present invention, the porous support layer is previously washed and then brought into contact with the aqueous solution.
According to an embodiment of the invention, the concentration of the polyamine in the aqueous phase solution is 1 to 5 wt%.
According to the embodiment of the invention, the contact time of the porous support layer and the aqueous phase solution is 5-300 s.
According to the embodiment of the invention, the material of the porous support layer is at least one selected from polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, polyvinylidene fluoride, polyethylene, polypropylene and polyacrylonitrile; and/or the polyamine is at least one selected from piperazine, dimethyl piperazine, 2-dimethyl piperazine, 2, 5-dimethyl piperazine and 2, 3-diamino piperazine.
According to the embodiment of the invention, the aqueous phase solution further comprises an acid absorbent and/or a catalyst, and the concentrations of the acid absorbent and the catalyst are respectively and independently 0.01-1 wt%.
According to an embodiment of the present invention, the acid absorbent is at least one selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, camphorsulfonic acid-triethylamine; and/or the catalyst is at least one selected from pyridine, imidazole, lutidine and 4-dimethylaminopyridine.
According to the embodiment of the invention, the mass ratio of the sulfonyl chloride to the polybasic acyl chloride is 1: 1-20: 1.
According to the embodiment of the invention, the concentration of the sulfonyl chloride and the concentration of the polyacyl chloride in the organic phase solution are respectively and independently 0.005-0.5 wt%.
According to the embodiment of the invention, the contact time of the porous support layer obtained in the step (1) and the organic phase solution is 5-900 s.
According to an embodiment of the present invention, the organic phase solution comprises an organic solvent, and the organic solvent is at least one selected from the group consisting of n-hexane, heptane, cyclohexane, ethylcyclohexane, Isopar G, Isopar E, and n-octane.
According to an embodiment of the present invention, the sulfonyl chloride is at least one selected from the group consisting of 1,3, 5-benzenetrisulfonyl chloride, 2,4, 6-trimethylbenzenetrisulfonyl chloride, 1,3, 6-naphthalenetrisulfonyl chloride and 2, 6-naphthalenedisulfonyl chloride.
According to an embodiment of the present invention, the poly-acid chloride is at least one selected from the group consisting of 1,3, 5-benzenetricarboxylic acid chloride, isophthaloyl dichloride, phthalic acid dichloride, terephthaloyl dichloride, and biphenyldicarbonyl dichloride.
According to the embodiment of the invention, in the step (3), the temperature of the heat treatment is 30-120 ℃ and the time is 1-10 min.
According to an embodiment of the present invention, the step (3) further includes: and repeatedly washing the acid-resistant composite nanofiltration membrane obtained by heat treatment by using deionized water, and storing the washed acid-resistant composite nanofiltration membrane into the deionized water.
According to another aspect of the invention, the invention provides an acid-resistant composite nanofiltration membrane. According to the embodiment of the invention, the acid-resistant composite nanofiltration membrane is obtained by adopting the method for preparing the acid-resistant composite nanofiltration membrane. Compared with the prior art, the acid-resistant composite nanofiltration membrane has good smoothness and density, good desalting performance and water flux performance, and good acid resistance, and the membrane performance is still stable after one month of treatment by adopting acid waste liquid, so that the acid-resistant composite nanofiltration membrane has a good application prospect in acid industrial wastewater treatment.
The invention has the following beneficial technical effects:
1. according to the invention, sulfonyl chloride with a better chemical inert functional group (such as a benzene ring and a heterocycle) is selected as a reaction monomer, and polyatomic acyl chloride with high reaction activity is mixed, so that an interface polymerization reaction can be carried out on a high-molecular porous supporting layer to form an ultrathin functional layer, the acid resistance of the nanofiltration membrane is improved, and meanwhile, the crosslinking degree of the interface polymerization reaction is also improved, so that the prepared functional layer is compact and the roughness is improved;
2. the preparation method disclosed by the invention is simple in process, and the interception rate of the acid-resistant composite nanofiltration membrane can be flexibly adjusted by adjusting the proportion of sulfonyl chloride and polybasic acyl chloride, so that the acid-resistant composite nanofiltration membrane has good desalting performance and water flux;
3. the acid-resistant composite nanofiltration membrane prepared by the invention has good desalting performance and water flux performance, and also has good stability, and the membrane performance is still stable after acid waste liquid is treated for one month, so that the acid-resistant composite nanofiltration membrane has good application prospect in acid industrial wastewater treatment.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
figure 1 is a flow diagram of a method for preparing an acid-resistant composite nanofiltration membrane according to one embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for preparing an acid-resistant composite nanofiltration membrane. According to an embodiment of the invention, with reference to fig. 1, the method comprises: (1) contacting the porous support layer with an aqueous solution containing a polyamine and drying; (2) contacting the porous support layer obtained in the step (1) with an organic phase solution containing sulfonyl chloride and a polybasic acyl chloride monomer, and drying; (3) and (3) carrying out heat treatment on the porous supporting layer obtained in the step (2) so as to obtain the acid-resistant composite nanofiltration membrane. The inventor finds that an acid-resistant material sulfonyl chloride can be selected as a reaction monomer in an organic phase solution to prepare the polysulfonamide nanofiltration membrane and improve the acid resistance of the nanofiltration membrane, and meanwhile, the polybasic acyl chloride is added into the organic phase solution in blending, so that the crosslinking degree in the interfacial polymerization reaction can be improved, the prepared functional layer is compact, the roughness is obviously improved, and the desalting performance and the water flux performance of the nanofiltration membrane can be further improved.
The method for preparing the acid-resistant composite nanofiltration membrane according to the above embodiment of the present invention is described in detail with reference to fig. 1.
S100: contacting the porous support layer with an aqueous solution containing a polyamine and drying
According to the embodiment of the invention, the porous support layer can be cleaned in advance, impurities on the surface of the porous support layer are removed, and then the porous support layer is contacted with the aqueous solution, so that the cleanliness of the functional layer formed on the surface of the porous support layer can be improved, and the bonding strength of the functional layer and the porous support layer can be further ensured. Further, the contacting may be performed by immersing the porous support layer in the aqueous solution, and after the contacting, the excess aqueous solution on the surface of the porous support layer may be removed by using an air knife.
According to an embodiment of the present invention, the concentration of the polyamine in the aqueous solution may be 1 to 5 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, and the inventors found that if the concentration of the polyamine in the aqueous solution is too low, the amount of the polyamine remaining on the surface of the porous support layer after contacting the aqueous solution is also small, and it is difficult to form a complete functional layer with good mechanical strength and structural stability; if the concentration of the polyamine in the aqueous phase solution is too high, the amount of the polyamine attached to the surface of the porous supporting layer is large, the subsequent reaction with sulfonyl chloride and polyacyl chloride only increases the thickness of a desalting layer, the influence on the desalting rate is not obvious, the flux is in a descending state, the flux descending rate is greater than the ascending of the desalting rate, and the polyamine in the aqueous phase solution is controlled within the concentration range, so that the functional layer with good mechanical strength, density, acid resistance and low roughness can be obtained, and the desalting performance and the water flux performance of the acid-resistant composite nanofiltration membrane are obviously improved.
According to another embodiment of the present invention, the contact time between the porous support layer and the aqueous solution may be 5 to 300s, for example, 10s, 20s, 30s, 50s, 80s, 100s, 150s, 200s, 250s, or 300s, and by controlling the contact time, the polyamine monomer in the aqueous solution can be ensured to be completely immersed into the pores of the porous support layer, and the subsequent interfacial polymerization reaction on the surface of the porous support layer can be ensured to be smoothly performed.
According to still another embodiment of the present invention, the porous support layer used in the present invention is made of a polymer material, wherein the kind of the polymer material is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the polymer material may be at least one selected from polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, polyvinylidene fluoride, polyethylene, polypropylene and polyacrylonitrile. For another example, the porous support layer may be a polysulfone porous support layer, a sulfonated polysulfone porous support layer, a polyethersulfone porous support layer, a sulfonated polyethersulfone porous support layer, a polyvinylidene fluoride porous support layer, a polyethylene porous support layer, a polypropylene porous support layer, a polyacrylonitrile porous support layer, or the like. Further, the kind of the polyamine in the present invention is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the polyamine may be at least one selected from piperazine, dimethylpiperazine, 2-dimethylpiperazine, 2, 5-dimethylpiperazine, and 2, 3-diaminopiperazine.
According to another embodiment of the present invention, the aqueous solution may further include an acid absorbent, wherein the concentration of the acid absorbent may be 0.01 to 1 wt%, for example, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, 0.9 wt%, or 1 wt%, and the inventors found that, when the reaction system of the present invention is used, a part of hydrogen chloride (HCl) is generated during the reaction process, and the polymerization of HCl at the primary interface may affect the forward direction of the reaction, so as to reduce the polymerization speed and the degree of polymerization crosslinking. The kind of the acid absorbent used in the present invention is not particularly limited, and those skilled in the art can select the acid absorbent according to actual needs, for example, the acid absorbent may be a pH buffer, an alkali or a strong alkali weak acid salt, and further, for example, at least one selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, and a camphorsulfonic acid-triethylamine system, thereby facilitating smooth proceeding of the subsequent interfacial polymerization reaction.
According to still another embodiment of the present invention, the aqueous solution may further include a catalyst, wherein the concentration of the catalyst may be 0.01 to 1 wt%, for example, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, 0.9 wt%, or 1 wt%, and the like, and by further adding the catalyst, the forward progress of the interfacial polymerization reaction between the polyamine and the sulfonyl chloride and the polyacyl chloride may be further promoted and the reaction rate may be increased. The kind of the catalyst used in the present invention is not particularly limited, and may be selected by those skilled in the art according to the actual needs, and for example, the catalyst may be at least one selected from pyridine, imidazole, lutidine and 4-dimethylaminopyridine.
S200: contacting the porous support layer obtained in step S100 with an organic phase solution containing sulfonyl chloride and a polybasic acid chloride monomer, and drying
According to the embodiment of the invention, the inventor finds that an ultrathin functional layer can be formed by combining the interfacial polymerization reaction of polyamine on a high-molecular porous supporting layer by selecting sulfonyl chloride with better chemical inert functional groups (such as benzene rings and heterocycles) as a reaction monomer and mixing polybasic acyl chloride with high reaction activity, so that the acid resistance of the nanofiltration membrane is improved, the crosslinking degree of the interfacial polymerization reaction is also improved, the prepared functional layer is compact, the roughness is improved, and the desalting performance and the water flux are effectively improved. Wherein the porous support layer with the polyamine formed on the surface can be immersed in the organic phase solution for a period of time and then dried until the surface is free of the organic phase solution.
According to a specific embodiment of the invention, the mass ratio of sulfonyl chloride to polyacyl chloride can be 1: 1-20: 1, for example, 1/1, 3/1, 5/1, 8/1, 12/1, 15/1 or 20/1, and the inventors find that the mass ratio of sulfonyl chloride to polyacyl chloride has very important influence on the surface roughness, desalination rate, water flux and performance stability of the finally prepared nanofiltration membrane, and if the mass ratio of sulfonyl chloride to polyacyl chloride is too small, the surface roughness of the nanofiltration membrane can be greatly reduced, so that the desalination rate is remarkably improved, but the water flux of the membrane is also obviously reduced; if the mass ratio of the two is too large, the water flux of the membrane can be greatly improved, but the desalination rate is also remarkably reduced, and the roughness of the membrane is also large. According to the invention, by controlling the mass ratio of sulfonyl chloride to polyacyl chloride to be in the range, the acid resistance of the nanofiltration membrane can be improved, and the crosslinking degree of interfacial polymerization reaction can be improved, so that the prepared functional layer is compact and the roughness is improved, for example, the root mean square roughness of the finally prepared acid-resistant composite nanofiltration membrane can be reduced to below 40Rms/nm, the desalination rate of the membrane can reach above 90%, and the water flux before acid treatment reaches 50-75L/m2h. Preferably, the mass ratio of sulfonyl chloride to polybasic acyl chloride can be 5: 1-20: 1, and the inventor finds that the mass ratio of sulfonyl chloride to polybasic acyl chloride can be controlled to be within the range of the mass ratioThe comprehensive performance of the nanofiltration membrane is further improved, the nanofiltration membrane has good performance stability, and after the nanofiltration membrane is treated by acid for one month, the performance of the membrane is still stable, for example, the root mean square roughness of the finally prepared acid-resistant composite nanofiltration membrane can be reduced to 22-36 Rms/nm, the desalination rate of the membrane can reach more than 95%, and the water flux can reach 55-70L/m2And h, more importantly, after the membrane is treated by the acid solution for 1 month, the desalination rate and the water flux of the membrane are still relatively stable, and the desalination rate is not lower than 95%.
According to another specific embodiment of the invention, the concentrations of sulfonyl chloride and poly-acyl chloride in the organic phase solution can be respectively and independently 0.005-0.5 wt%, and the inventor finds that if the concentrations of sulfonyl chloride and poly-acyl chloride are too low, it is difficult to make the polyamine on the surface of the porous support layer fully react to prepare a complete functional layer, and if the concentrations of sulfonyl chloride and poly-acyl chloride are too high, the thickness of the prepared functional layer is likely to be increased, so that the flux of the nanofiltration membrane is obviously reduced.
According to another embodiment of the present invention, the contact time between the porous support layer with the polyamine formed on the surface and the organic phase solution may be 5 to 900s, for example, 10s, 20s, 30s, 50s, 80s, 100s, 150s, 200s, 250s, 300s, 500s, 700s, 900s, and the like, and by controlling the contact time, it is ensured that the sulfonyl chloride and the poly-acid chloride in the organic phase solution can uniformly and sufficiently contact with the polyamine on the surface of the porous support layer and undergo an interfacial polymerization reaction.
According to still another embodiment of the present invention, the kind of the organic solvent used in the organic phase solution is not particularly limited and may be selected by those skilled in the art according to actual needs, for example, the organic solvent may be at least one selected from n-hexane, heptane, cyclohexane, ethylcyclohexane, Isopar G, Isopar E and n-octane. Further, the types of sulfonyl chloride and poly-acyl chloride used in the present invention are not particularly limited, and those skilled in the art can select them according to actual needs, for example, the sulfonyl chloride can be at least one selected from 1,3, 5-benzene trisulfonyl chloride, 2,4, 6-trimethyl benzene sulfonyl chloride, 1,3, 6-naphthalene trisulfonyl chloride and 2, 6-naphthalene disulfonyl chloride, and the poly-acyl chloride can be at least one selected from 1,3, 5-benzene trisulfonyl chloride, isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride and biphenyldicarbonyl chloride, so that the finally obtained acid-resistant composite nanofiltration membrane can have functional layers with better mechanical strength, acid resistance and lower roughness, and the desalination performance and water flux performance of the membrane can be significantly improved.
S300: carrying out heat treatment on the porous supporting layer obtained in the step S200 to obtain the acid-resistant composite nanofiltration membrane
According to the embodiment of the invention, the porous support layer contacted with the organic phase solution can be placed in an oven for heat treatment so as to further promote the interfacial polymerization reaction and enable the functional layer to form a net-shaped structure through cross-linking polymerization, wherein deionized water can be adopted for repeated washing after the heat treatment is finished, and the washed acid-resistant composite nanofiltration membrane is stored in the deionized water. Further, the temperature of the heat treatment can be 30 to 120 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or 110 ℃ and the like, and the time can be 1 to 10min, for example, 2min, 3min, 5min, 7min or 9min and the like, the heat treatment can not only further promote the crosslinking reaction of the membrane surface layer, but also influence the rearrangement of polymer molecular chain segments, and can promote the removal of organic solvent, and finally influence the aperture and pore structure of the functional surface layer, the too high heat treatment temperature can cause the too high crosslinking degree of the functional surface layer, the increase of the membrane thickness causes the reduction of water flux, by controlling the temperature and the time of the heat treatment, not only the interfacial polymerization reaction rate can be improved, but also the crosslinking polymerization of the functional layer can be facilitated, so that the functional layer with better mechanical strength, compactness, acid resistance and lower roughness can be obtained, the desalting performance and the water flux performance of the acid-resistant composite nanofiltration membrane are obviously improved.
According to a specific embodiment of the invention, when the acid-resistant composite nanofiltration membrane is prepared, the porous support layer can be a polysulfone porous support layer; the polyamine in the aqueous phase solution can be piperazine with the content of 1-5 wt%, the aqueous phase solution can comprise an acid absorbent camphorsulfonic acid-triethylamine system and a catalyst of 4-dimethylamino pyridine, the solvent in the organic phase solution can be Isopar G, the sulfonyl chloride can be 1,3, 6-naphthalene trisulfonyl chloride with the mass concentration of 0.01-0.5%, and the polybasic acyl chloride can be 1,3, 5-benzene tricarboxy chloride with the mass concentration of 0.01-0.5%. Therefore, the comprehensive performance and the performance stability of the finally prepared acid-resistant composite nanofiltration membrane can be further ensured.
In summary, the acid-resistant composite nanofiltration membrane prepared by the embodiment of the invention has the following advantages: 1. sulfonyl chloride with better chemical inert functional groups (such as benzene rings and heterocycles) is selected as a reaction monomer, and polybasic acyl chloride with high reaction activity is mixed, so that an interface polymerization reaction can be carried out on a high-molecular porous supporting layer to form an ultrathin functional layer, the acid resistance of the nanofiltration membrane is improved, and the crosslinking degree of the interface polymerization reaction is also improved, so that the prepared functional layer is compact and the roughness is improved; 2. the preparation method is simple in process, and the interception rate of the acid-resistant composite nanofiltration membrane can be flexibly adjusted by adjusting the proportion of sulfonyl chloride and polybasic acyl chloride, so that the acid-resistant composite nanofiltration membrane has good desalting performance and water flux; 3. the acid-resistant composite nanofiltration membrane prepared by the method has good desalting performance and water flux performance, and also has good stability, and the membrane performance is still stable after acid waste liquid is treated for one month, so that the acid-resistant composite nanofiltration membrane has good application prospect in acid industrial wastewater treatment.
According to another aspect of the invention, the invention provides an acid-resistant composite nanofiltration membrane. According to the embodiment of the invention, the acid-resistant composite nanofiltration membrane is obtained by adopting the method for preparing the acid-resistant composite nanofiltration membrane. Compared with the prior art, the acid-resistant composite nanofiltration membrane has good smoothness and density, good desalting performance and water flux performance, and good acid resistance, and the membrane performance is still stable after one month of treatment by adopting acid waste liquid, so that the acid-resistant composite nanofiltration membrane has a good application prospect in acid industrial wastewater treatment. It should be noted that the features and effects described for the above method for preparing the acid-resistant composite nanofiltration membrane are also applicable to the acid-resistant composite nanofiltration membrane, and are not described in detail herein.
The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The general method comprises the following steps:
the method for preparing the acid-resistant composite nanofiltration membrane comprises the following steps: selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the contact time is 1min, taking out and removing the excess aqueous phase solution on the surface, then immersing the bottom membrane into an organic phase solution of Isopar G containing 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene trimethyloyl chloride, wherein the contact time is 3min, allowing the piperazine, the 1,3, 6-naphthalene trisulfonyl chloride and the 1,3, 5-benzene trimethyloyl chloride to perform interfacial polymerization reaction, performing heat treatment for 3min in an oven at 100 ℃, further performing interfacial polymerization reaction, and finally forming the composite nanofiltration membrane.
And (3) testing the water flux and the salt rejection performance of the composite nanofiltration membrane: the test is completed by a membrane detection table, the test solution is 2000ppm magnesium sulfate aqueous solution, the pH value is 6.5-7.5, the operation temperature is 25 ℃, and the water flux and the desalination rate of the membrane are tested after the membrane is operated for 30min under the condition of 0.7MPa operation pressure.
The acid treatment conditions used in the acid resistance test of the composite nanofiltration membrane are as follows: the membrane is soaked in 10% sulfuric acid solution for 1 month at 25 deg.C. And repeatedly washing the membrane subjected to acid treatment by using deionized water to remove free acid remained in the membrane until the pH value of the cleaning solution is stable, and testing the desalination rate and water flux of the nanofiltration membrane.
Example 1
Selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the mass concentration of the piperazine is 2%, the mass concentrations of camphorsulfonic acid, triethylamine and 4-dimethylaminopyridine are 4.4%, 2.2% and 0.4%, respectively, the contact time with the aqueous phase solution is 1min, and taking out and removing the excess aqueous phase solution on the surface; and then immersing the membrane into an organic phase solution of Isopar G containing 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene tricarboxychloride, wherein the mass concentration of the two is 0.2% and 0.01% in sequence, the contact time is 3min, allowing piperazine, 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene tricarboxychloride to perform interfacial polymerization reaction, performing heat treatment in an oven at 100 ℃ for 3min, further performing interfacial polymerization reaction, and finally forming the composite nanofiltration membrane.
Example 2
Selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the mass concentration of the piperazine is 2%, the mass concentrations of camphorsulfonic acid, triethylamine and 4-dimethylaminopyridine are 4.4%, 2.2% and 0.1%, respectively, the contact time with the aqueous phase solution is 1min, and taking out and removing the excess aqueous phase solution on the surface; and then immersing the membrane into an organic phase solution of Isopar G containing 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene tricarboxychloride, wherein the mass concentration of the two is 0.2 percent and 0.02 percent in sequence, the contact time is 3min, piperazine, the 1,3, 6-naphthalene trisulfonyl chloride and the 1,3, 5-benzene tricarboxychloride are subjected to interfacial polymerization reaction, the membrane is subjected to heat treatment in an oven at 100 ℃ for 3min, the interfacial polymerization reaction is further performed, and finally the composite nanofiltration membrane is formed.
Example 3
Selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the mass concentration of the piperazine is 2%, the mass concentrations of camphorsulfonic acid, triethylamine and 4-dimethylaminopyridine are 4.4%, 2.2% and 0.1%, respectively, the contact time with the aqueous phase solution is 1min, and taking out and removing the excess aqueous phase solution on the surface; and then immersing the membrane into an organic phase solution of Isopar G containing 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene tricarboxychloride, wherein the mass concentration of the two is 0.2 percent and 0.04 percent in sequence, the contact time is 3min, piperazine, the 1,3, 6-naphthalene trisulfonyl chloride and the 1,3, 5-benzene tricarboxychloride are subjected to interfacial polymerization reaction, the membrane is subjected to heat treatment in an oven at 100 ℃ for 3min, the interfacial polymerization reaction is further performed, and finally the composite nanofiltration membrane is formed.
Example 4
Selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the mass concentration of the piperazine is 2%, the mass concentrations of camphorsulfonic acid, triethylamine and 4-dimethylaminopyridine in the aqueous phase solution are respectively 4.4%, 2.2% and 0.1%, and the contact time with the aqueous phase solution is 1min, and taking out and removing the excess aqueous phase solution on the surface; and then immersing the membrane into an organic phase solution of Isopar G containing 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene tricarboxychloride, wherein the mass concentration of the two is 0.1 percent and 0.05 percent in sequence, the contact time is 3min, piperazine, the 1,3, 6-naphthalene trisulfonyl chloride and the 1,3, 5-benzene tricarboxychloride are subjected to interfacial polymerization reaction, the membrane is subjected to heat treatment in an oven at 100 ℃ for 3min, the interfacial polymerization reaction is further performed, and finally the composite nanofiltration membrane is formed.
Example 5
Selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the mass concentration of the piperazine is 2%, the mass concentrations of camphorsulfonic acid, triethylamine and 4-dimethylaminopyridine are 4.4%, 2.2% and 0.1%, respectively, the contact time with the aqueous phase solution is 1min, and taking out and removing the excess aqueous phase solution on the surface; and then immersing the membrane into an organic phase solution of Isopar G containing 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene tricarboxychloride, wherein the mass concentration of the two is 0.1 percent and 0.1 percent in sequence, the contact time is 3min, allowing piperazine, 1,3, 6-naphthalene trisulfonyl chloride and 1,3, 5-benzene tricarboxychloride to perform interfacial polymerization reaction, performing heat treatment in an oven at 100 ℃ for 3min, further performing interfacial polymerization reaction, and finally forming the composite nanofiltration membrane.
Comparative example 1
Selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the mass concentration of the piperazine is 2%, the mass concentrations of camphorsulfonic acid, triethylamine and 4-dimethylaminopyridine are 4.4%, 2.2% and 0.1%, respectively, the contact time with the aqueous phase solution is 1min, and taking out and removing the excess aqueous phase solution on the surface; and then immersing the membrane into Isopar G organic phase solution containing 1,3, 6-naphthalene trisulfonyl chloride, wherein the mass concentration of the 1,3, 6-naphthalene trisulfonyl chloride is 0.2%, the contact time is 3min, allowing piperazine and the 1,3, 6-naphthalene trisulfonyl chloride to perform interfacial polymerization reaction, performing heat treatment for 3min in a 100 ℃ oven, further performing interfacial polymerization reaction, and finally forming the composite nanofiltration membrane.
Comparative example 2
Selecting a polysulfone porous supporting layer as a bottom membrane, cleaning the bottom membrane with deionized water before use to remove surface impurities, immersing the bottom membrane into an aqueous phase solution containing piperazine, wherein the mass concentration of piperazine is 2%, the mass concentrations of camphorsulfonic acid and triethylamine are 4.4% and 2.2%, respectively, the contact time with the aqueous phase solution is 1min, and taking out and removing the excess aqueous phase solution on the surface; and then immersing the membrane into an organic phase solution of Isopar G containing 1,3, 5-benzene tricarbochloride, wherein the mass concentration of the 1,3, 5-benzene tricarbochloride is 0.1%, the contact time is 20S, piperazine and the 1,3, 5-benzene tricarbochloride are subjected to interfacial polymerization reaction, the membrane is subjected to heat treatment for 3min in an oven at 100 ℃, the interfacial polymerization reaction is further carried out, and finally the composite nanofiltration membrane is formed.
The surface roughness, the salt rejection, the water flux and the acid resistance of the composite nanofiltration membranes prepared in examples 1 to 5 and comparative examples 1 to 2 were measured, and the test results are shown in table 1.
TABLE 1 Performance test results of composite nanofiltration membranes prepared in examples 1 to 5 and comparative examples 1 to 2
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
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| CN114749035A (en) * | 2022-04-14 | 2022-07-15 | 浙江美易膜科技有限公司 | Low-pressure large-flux hollow fiber nanofiltration membrane as well as preparation method and application thereof |
| CN115608176A (en) * | 2022-11-11 | 2023-01-17 | 中国科学院赣江创新研究院 | Structure of high-performance polysulfonamide acid-resistant nanofiltration membrane and preparation method thereof |
| CN115646212A (en) * | 2022-12-27 | 2023-01-31 | 湖南沁森高科新材料有限公司 | Nanofiltration membrane and preparation method thereof |
| CN119236707A (en) * | 2024-12-05 | 2025-01-03 | 山东海化集团有限公司 | Preparation method of a high-pressure and high-salt concentration composite nanofiltration membrane and nanofiltration membrane thereof |
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| CN111686592A (en) * | 2019-03-11 | 2020-09-22 | 湖州欧美新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN113083035A (en) * | 2021-04-12 | 2021-07-09 | 江南大学 | Ultra-low pressure composite nanofiltration membrane and preparation method thereof |
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| CN111686592A (en) * | 2019-03-11 | 2020-09-22 | 湖州欧美新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN113083035A (en) * | 2021-04-12 | 2021-07-09 | 江南大学 | Ultra-low pressure composite nanofiltration membrane and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114749035A (en) * | 2022-04-14 | 2022-07-15 | 浙江美易膜科技有限公司 | Low-pressure large-flux hollow fiber nanofiltration membrane as well as preparation method and application thereof |
| US11878271B1 (en) | 2022-04-14 | 2024-01-23 | Harris Membrane Clean Technology Inc. | Low-pressure high-flux hollow fiber nanofiltration (NF) membrane, and preparation method and use thereof |
| CN115608176A (en) * | 2022-11-11 | 2023-01-17 | 中国科学院赣江创新研究院 | Structure of high-performance polysulfonamide acid-resistant nanofiltration membrane and preparation method thereof |
| CN115608176B (en) * | 2022-11-11 | 2023-11-10 | 中国科学院赣江创新研究院 | Structure of high-performance polyamide acid-resistant nanofiltration membrane and preparation method thereof |
| CN115646212A (en) * | 2022-12-27 | 2023-01-31 | 湖南沁森高科新材料有限公司 | Nanofiltration membrane and preparation method thereof |
| CN115646212B (en) * | 2022-12-27 | 2023-03-10 | 湖南沁森高科新材料有限公司 | Nanofiltration membrane and preparation method thereof |
| CN119236707A (en) * | 2024-12-05 | 2025-01-03 | 山东海化集团有限公司 | Preparation method of a high-pressure and high-salt concentration composite nanofiltration membrane and nanofiltration membrane thereof |
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