CN113813798A - Cobalt @ iron bimetallic hydroxide nanoparticle-doped mixed matrix ultrafiltration membrane and preparation method thereof - Google Patents
Cobalt @ iron bimetallic hydroxide nanoparticle-doped mixed matrix ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN113813798A CN113813798A CN202111142559.4A CN202111142559A CN113813798A CN 113813798 A CN113813798 A CN 113813798A CN 202111142559 A CN202111142559 A CN 202111142559A CN 113813798 A CN113813798 A CN 113813798A
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- 239000012528 membrane Substances 0.000 title claims abstract description 171
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 89
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 47
- 239000011159 matrix material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 15
- 239000000243 solution Substances 0.000 claims abstract description 105
- 239000002033 PVDF binder Substances 0.000 claims abstract description 73
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 72
- 239000000693 micelle Substances 0.000 claims abstract description 67
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 67
- 230000002441 reversible effect Effects 0.000 claims abstract description 67
- 238000005266 casting Methods 0.000 claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000004064 cosurfactant Substances 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000004692 metal hydroxides Chemical class 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 57
- 230000004907 flux Effects 0.000 abstract description 22
- 239000000839 emulsion Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 37
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- 239000008213 purified water Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 238000002791 soaking Methods 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 13
- 239000002131 composite material Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 8
- 229940098773 bovine serum albumin Drugs 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229960000892 attapulgite Drugs 0.000 description 6
- 229910052625 palygorskite Inorganic materials 0.000 description 6
- 230000033558 biomineral tissue development Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 239000002122 magnetic nanoparticle Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000614 phase inversion technique Methods 0.000 description 3
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a mixed matrix ultrafiltration membrane doped with cobalt @ iron double-metal hydroxide nanoparticles and a preparation method thereof, wherein (1) an oil phase medium, a surfactant and a cosurfactant are mixed and stirred to obtain a mixed solution A; (2) adding Co into the mixed solution A2+Inorganic salts and Fe3+Mixed aqueous solution of inorganic salt to form a mixed solution containing Co2+And Fe3+The reverse micelle microemulsion B of (1); (3) dropwise adding ammonia water into the reverse micelle microemulsion B under stirring to obtain a reverse micelle microemulsion C containing the cobalt @ iron double-metal hydroxide nano particles; (4) mixing the reverse micelle microemulsion C with a polyvinylidene fluoride solution according to a ratio to obtain a casting solution D; (5) preparation of film casting solution DAnd obtaining the mixed matrix ultrafiltration membrane. The invention utilizes the hydrophilicity of the nano particles in the emulsion containing the cobalt @ iron double-metal hydroxide nano particles, the amphipathy of the surfactant and the synergistic effect thereof to improve the pollution resistance and the water flux of the mixed matrix ultrafiltration membrane.
Description
Technical Field
The invention belongs to the technical field of nano materials and membrane separation, and particularly relates to a preparation method of a cobalt @ iron double-metal hydroxide nanoparticle-doped mixed matrix ultrafiltration membrane with high water flux and anti-pollution performance.
Background
Polyvinylidene fluoride is a commonly used ultrafiltration membrane material at present, and due to the hydrophobicity of the polyvinylidene fluoride ultrafiltration membrane, organic matters, microorganisms and the like in water are easily adsorbed and deposited on the surface of the membrane in the use process of the polyvinylidene fluoride ultrafiltration membrane, so that membrane pores are blocked, and the pollution of the membrane is caused. Membrane pollution can cause attenuation of membrane flux, so that the polluted membrane needs to be cleaned by adopting physical, chemical and other methods; in addition, some contamination will cause irreversible attenuation of the membrane flux to some extent. These will greatly increase the operating costs of the operation and shorten the useful life of the membrane. Therefore, the improvement of the anti-contamination performance is one of the important measures for the development of the application of the ultrafiltration membrane.
In recent years, the construction of high-performance mixed matrix ultrafiltration membranes by doping inorganic nanomaterials such as metal nanoparticles has become a research hotspot in the technical field of membrane separation. For example, chinese patent application No. CN201811118802.7 discloses a method for preparing an anti-pollution polyvinylidene fluoride hybrid ultrafiltration membrane, which comprises adding dry powder of poly-tannic acid/polyethyleneimine/titanium dioxide composite nanoparticles into N-methyl pyrrolidone for uniform dispersion, adding polyvinylidene fluoride and polyethylene glycol, stirring and dissolving to form a membrane casting solution, and defoaming the membrane casting solution; and pouring the defoamed membrane casting solution on a glass plate, scraping and coating the membrane casting solution into a continuous and uniform flat liquid membrane by a scraper, quickly immersing the flat liquid membrane into a coagulating bath, soaking until the liquid membrane is completely cured, washing the cured membrane in deionized water to remove residual N-methyl pyrrolidone, and finally drying the washed membrane to obtain the anti-pollution polyvinylidene fluoride hybrid ultrafiltration membrane. The invention utilizes the modifier property of the organic-inorganic composite nano material to carry out in-situ blending modification on the ultrafiltration membrane, can synchronously improve the anti-pollution performance and the membrane flux of the membrane and avoid the generation of structural defects in the membrane.
The Chinese patent application with the application number of CN201710769750.9 discloses a supported Ag-TiO2The preparation method and the application of the PES ultrafiltration membrane. The PES ultrafiltration membrane is immersed in the Ag TiO2In the composite sol, Ag and TiO loaded on the surface of the film can be obtained2The PES ultrafiltration membrane of (1). The invention is loaded with Ag and TiO2The PES ultrafiltration membrane has Ag and TiO on the surface2The photocatalytic material is adopted, so that the water contact angle of the ultrafiltration membrane is reduced, the membrane pollution is favorably slowed down, and the membrane flux is increased; in addition, under the irradiation of visible light, Ag and TiO on the surface of the film2The photocatalytic material can degrade pollutants on the surface of the PES ultrafiltration membrane, so that the pollutants on the surface of the PES ultrafiltration membrane can be further slowed downMembrane fouling, increasing membrane flux.
The Chinese patent application with the application number of CN201910166789.0 discloses a polysulfone/nano titanium dioxide organic-inorganic hybrid hollow fiber ultrafiltration membrane and a preparation method thereof. The inorganic network and the titanium dioxide nano particles are introduced into the polysulfone hollow fiber ultrafiltration membrane by a sol-gel method, so that the hydrophilicity of the polysulfone membrane is improved, the pollution resistance of the membrane is improved, the mechanical strength of the membrane is enhanced, and the service life of the membrane is prolonged.
The Chinese patent application with the application number of CN201910006571.9 provides Ag @ NH2MIL 125/polyarylethersulfone hybridized compact reactive ultrafiltration membrane and a preparation method thereof. Firstly, preparing a sunlight response type photocatalytic material Ag @ NH2MIL 125, introducing the photocatalytic material into a polyarylethersulfone molecular chain structure by molecular design and utilizing chemical bond action to synthesize Ag @ NH2MIL 125/polyarylethersulfone hybrid material, and a compact reactive ultrafiltration membrane is prepared from the material by using a dipping precipitation phase inversion method. The ultrafiltration membrane shows excellent separation performance and high-efficiency sunlight response self-cleaning capability in the treatment process of dye wastewater, and has important significance and wide application prospect in the technical field of water treatment membrane separation.
The Chinese patent application with the application number of CN202010182856.0 discloses polyvinylidene fluoride/Fe3O4The attapulgite composite ultrafiltration membrane and the preparation method thereof comprise the following steps: the ferroferric oxide nano particles are immobilized on the surface of the attapulgite nano fiber to obtain the super-hydrophilic Fe with a unique screw-thread steel bar-shaped structure3O4An attapulgite nanocomposite; mixing polyvinylidene fluoride powder and Fe3O4Preparing a casting solution from attapulgite nano composite particles, a pore-forming agent polyethylene glycol 400 and triethyl phosphate, and uniformly stirring; defoaming, scraping, soaking and naturally airing the casting solution to obtain the vinylidene fluoride/Fe3O4An attapulgite composite ultrafiltration membrane. The invention utilizes Fe3O4The unique screw-thread-like steel structure and super-hydrophilicity of attapulgite (MGPS) effectively improve the toughness, stability, permeation flux and resistance of a polymer filmAnd (4) pollution.
The patent application document of the Chinese invention with the application number of CN201910905439.1 relates to a preparation method and application of an SGO ZnO PSF composite ultrafiltration membrane. According to the invention, ZnO nanoparticles are dispersed on the SGO sheet layer by an immersion precipitation phase inversion method to prepare the SGO ZnO composite nanomaterial blend modified PSF ultrafiltration membrane, so that the pollution of humic acid with negative electricity to the membrane can be effectively prevented, and the PSF ultrafiltration membrane is used for separating humic acid in water. The SGO ZnO PSF composite ultrafiltration membrane prepared by the method has good pollution resistance, and simultaneously solves the problems of easy agglomeration and the like caused by inorganic material doping modification, and the modified composite membrane can effectively prevent humic acid with negative electricity from polluting the membrane.
The Chinese patent application with the application number of CN201911253666.7 discloses a preparation method of an inorganic nano homogeneous hybrid PVDF (polyvinylidene fluoride) super-hydrophilic ultrafiltration membrane, which comprises the steps of preparing an acrylic acid grafted PVDF membrane casting solution, blending and doping metal ions, carrying out in-situ mineralization and phase inversion to form a membrane, and thus obtaining the in-situ mineralized inorganic nano homogeneous hybrid PVDF ultrafiltration membrane with super-hydrophilicity. According to the method, multiple processes of grafting modification, metal ion coordination homogeneous phase doping, in-situ mineralization reaction and the like are continuously implemented, the inorganic nano-hybrid PVDF ultrafiltration membrane prepared by the method has better mechanical property and compressive tightness, the membrane flux attenuation is reduced, the mineralization efficiency of the nano particles is high, the mineralization degree is large, the distribution is uniform, and the problems that metal ions are easy to lose, the distribution of the inorganic nano particles is nonuniform and the like in the traditional mineralization modification are effectively solved.
The Chinese invention patent application with the application number of CN202010320430.7 discloses a strong anti-pollution composite gradient ultrafiltration membrane and a preparation method thereof, wherein the ultrafiltration membrane is prepared by chemically bonding the surface of graphene oxide with magnetic nanoparticles to form a graphene oxide magnetic nanoparticle hybrid, then uniformly dispersing the graphene oxide magnetic nanoparticle hybrid, organic fluorosilane and a pore-forming agent in a polysulfone solution, adopting the solution to cast a membrane-forming method, and carrying out magnetic field assisted non-solvent induced phase conversion. Can overcome the defects that organic pollutants are easy to adhere to and block membrane pores, the separation efficiency is low, the membrane is not easy to clean, the flux recovery rate is low and the like in the ultrafiltration separation process of the traditional polymer membrane material.
Disclosure of Invention
The invention provides a cobalt @ iron double-metal hydroxide nanoparticle-doped mixed matrix ultrafiltration membrane and a preparation method thereof.
A cobalt @ iron double metal hydroxide nanoparticle-doped mixed matrix ultrafiltration membrane and a preparation method thereof comprise the following steps:
(1) mixing and stirring the oil phase medium, the surfactant and the cosurfactant to obtain a mixed solution A.
Optionally, the oil phase medium is a naphthenic organic matter, preferably cyclohexane.
Optionally, the surfactant is an alkylphenol polyoxyethylene ether organic compound, preferably octylphenol polyoxyethylene ether.
Optionally, the cosurfactant is an alcohol organic substance, preferably n-butanol.
Optionally, the oil phase medium, the surfactant and the cosurfactant are mixed, and the volume ratio of the oil phase medium, the surfactant and the cosurfactant is (2-10): 1: (0.3-1), preferably (3-6): 1: (0.3-0.7).
Most preferably, the volume ratio of the cyclohexane to the octyl phenol polyoxyethylene ether to the n-butyl alcohol is 4:1: 0.5.
(2) Dropwise adding Co-containing solution into the mixed solution A under stirring2+And Fe3+Forming a mixed aqueous solution containing Co2+And Fe3+The reverse micelle microemulsion B of (a).
Optionally, the material containing Co2+And Fe3+In the inorganic salt mixed aqueous solution of (2), Co2+The salt being CoCl2Or CoSO4；Fe3+The salt being FeCl3Or Fe2(SO4)3。
Optionally, Co in the mixed aqueous solution2+And Fe3+Are respectively 0.2 to 0.4mol/L and 0.2 to 0.4mol/L, and further preferably, the Co is2+Is 0.2mol/L, the concentration of the Fe3+The concentration of (2) is 0.4 mol/L.
Optionally, the volume of the surfactant in the mixed aqueous solution and the mixed solution A is 1 (1.5-5), and preferably 1 (2-3.5).
Further, the Co2+Is 0.2mol/L, the concentration of the Fe3+The concentration of (A) is 0.4 mol/L; the volume of the surfactant in the mixed aqueous solution and the mixed solution A is 1: (2.2-2.4).
(3) To obtain a catalyst containing Co2+And Fe3+And dropwise adding ammonia water into the reverse micelle microemulsion B, and stirring to obtain a reverse micelle microemulsion C containing the cobalt @ iron double-metal hydroxide nanoparticles.
Optionally, the concentration of the ammonia water is 6-8 mol/L, the mole number of the dropwise added ammonia and the Co-containing ammonia2+And Fe3+Reverse micelle microemulsion B of (1)2+And Fe3+The ratio of the total number of moles of (2-3): 1, preferably 3: 1.
(4) and (3) uniformly mixing the reverse micelle microemulsion C containing the cobalt @ iron bimetal hydroxide nano particles with a polyvinylidene fluoride solution to obtain a casting solution D.
Optionally, in the polyvinylidene fluoride solution, the mass, mass and volume ratio of polyvinylidene fluoride, polyethylene glycol and N, N' -dimethylacetamide is (150-250) g and (30-50) g and 1L, and preferably (180-220) g and (35-45) g and 1L.
The polyvinylidene fluoride is a commercially available membrane material.
The polyethylene glycol is a commercial material, and the molecular weight is 400-4000 g/mol, preferably 2000 g/mol.
The N, N' -dimethylacetamide is a commercial solvent.
Optionally, the casting solution D contains reverse micelle microemulsion C containing cobalt @ iron double-metal hydroxide nanoparticles and a polyvinylidene fluoride solution, and the mass ratio of the mixture to the polyvinylidene fluoride solution is 1 (5-20). Preferably 1 (5-17). Further preferably 1 (5-15).
(5) And (3) preparing the cobalt @ iron double metal hydroxide doped mixed matrix ultrafiltration membrane by using the membrane casting solution D through an immersion precipitation phase conversion method.
Optionally, the immersion precipitation phase inversion method comprises:
uniformly coating the casting solution D on a flat and clean glass plate, wherein the coating thickness is 200 mu m; and immersing the glass plate coated with the film in purified water at 25 ℃ after 1 minute, taking out the film automatically falling off from the glass plate after 1 hour, putting the film into a container filled with a large amount of purified water, soaking for 24 hours, taking out, and naturally airing to obtain the cobalt @ iron double-metal hydroxide doped mixed matrix ultrafiltration membrane.
In each preparation step, further preferred combination conditions are:
in the step (1), the volume ratio of the cyclohexane to the octyl phenol polyoxyethylene ether to the n-butyl alcohol is 4:1: 0.5;
said Co in step (2)2+Is 0.2mol/L, the concentration of the Fe3+The concentration of (A) is 0.4 mol/L; the volume of the surfactant in the mixed aqueous solution and the mixed solution A is 1: (2.2-2.4);
the concentration of the ammonia water in the step (3) is 6-8 mol/L, the mole number of the dropwise added ammonia and the Co-contained ammonia2+And Fe3+Reverse micelle microemulsion B of (1)2+And Fe3+The ratio of the sum of the moles of (a) is 3: 1;
in the polyvinylidene fluoride solution in the step (4), the mass and the volume ratio of the polyvinylidene fluoride, the polyethylene glycol and the N, N' -dimethylacetamide are 200g:40g: 1L; the mass ratio of the reverse micelle microemulsion C to the polyvinylidene fluoride solution is 1 (8-10).
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) the invention adopts the cobalt @ iron double-metal hydroxide nano particles synthesized by the reverse micelle microemulsion in situ reduction, and the nano particles have smaller particle size and controllable structure.
(2) The emulsion containing the cobalt @ iron double-metal hydroxide nano particles and the polyvinylidene fluoride solution are blended to prepare the mixed matrix ultrafiltration membrane, the method is simple and convenient, the nano particles can be uniformly dispersed in the polyvinylidene fluoride matrix, and a scanning electron microscope (shown in figure 1) of the mixed matrix membrane (such as example 2) shows that the double-metal hydroxide nano particles are uniformly dispersed in the PVDF matrix, and the uniform dispersion is favorable for the double-metal hydroxide nano particles to play a greater role in improving the membrane performance.
(3) The anti-pollution performance and water flux of the mixed matrix ultrafiltration membrane are improved by utilizing the hydrophilicity of the nano particles in the emulsion containing the cobalt @ iron double metal hydroxide nano particles, the amphipathy of the surfactant and the synergistic effect of the surfactant.
Drawings
FIG. 1 is a scanning electron micrograph of a mixed matrix ultrafiltration membrane prepared in example 2.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying examples, in which some, but not all examples of the invention are shown. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The starting materials used in the following examples are commercially available products unless otherwise specified.
Example 1
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
② dripping 30mLCoCl into the mixed liquid prepared in the step I2And FeCl3The mixed aqueous solution of (1), CoCl of the mixed aqueous solution2And FeCl3The concentration is respectively 0.2mol/L and 0.4mol/L, and the mixture is stirred for 15 minutes to obtain the Co-containing material2+And Fe3+The reverse micelle microemulsion of (1).
And thirdly, 9mL of ammonia water with the concentration of 6mol/L is dripped into the reverse micelle microemulsion prepared in the second step, and the mixture is stirred for 0.5 hour to prepare the reverse micelle microemulsion containing the cobalt @ iron double-metal hydroxide nano particles.
Mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 900g of polyvinylidene fluoride solution with 100g of reverse micelle microemulsion prepared in the step (c), and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Fifthly, standing and defoaming the casting solution prepared in the step IV, uniformly coating the casting solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, rapidly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a membrane, transferring the membrane to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the membrane after soaking for 24 hours, and naturally airing the membrane to obtain the cobalt @ iron double-metal hydroxide doped mixed matrix ultrafiltration membrane.
Example 2
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
② dripping 35mLCoCl into the mixed liquid prepared in the step I2And FeCl3The mixed aqueous solution of (1), CoCl of the mixed aqueous solution2And FeCl3The concentration is respectively 0.2mol/L and 0.4mol/L, and the mixture is stirred for 15 minutes to obtain the Co-containing material2+And Fe3+The reverse micelle microemulsion of (1).
And thirdly, 9mL of ammonia water with the concentration of 7mol/L is dripped into the reverse micelle microemulsion prepared in the second step, and the mixture is stirred for 0.5 hour to prepare the reverse micelle microemulsion containing the cobalt @ iron double-metal hydroxide nano particles.
Mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 900g of polyvinylidene fluoride solution with 100g of reverse micelle microemulsion prepared in the step (c), and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Fifthly, standing and defoaming the casting solution prepared in the step IV, uniformly coating the casting solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, rapidly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a membrane, transferring the membrane to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the membrane after soaking for 24 hours, and naturally airing the membrane to obtain the cobalt @ iron double-metal hydroxide doped mixed matrix ultrafiltration membrane. The scanning electron micrograph of the mixed matrix ultrafiltration membrane prepared in this example is shown in fig. 1, which shows that the double metal hydroxide nanoparticles are uniformly dispersed in the PVDF matrix.
Example 3
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
② dripping 40mLCoCl into the mixed liquid prepared in the step I2And FeCl3The mixed aqueous solution of (1), CoCl of the mixed aqueous solution2And FeCl3The concentration is respectively 0.2mol/L and 0.4mol/L, and the mixture is stirred for 15 minutes to obtain the Co-containing material2+And Fe3+The reverse micelle microemulsion of (1).
And thirdly, 9mL of ammonia water with the concentration of 8mol/L is dripped into the reverse micelle microemulsion prepared in the second step, and the mixture is stirred for 0.5 hour to prepare the reverse micelle microemulsion containing the cobalt @ iron double-metal hydroxide nano particles.
Mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 900g of polyvinylidene fluoride solution with 100g of reverse micelle microemulsion prepared in the third step, and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Fifthly, standing and defoaming the casting solution prepared in the step IV, uniformly coating the casting solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, rapidly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a membrane, transferring the membrane to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the membrane after soaking for 24 hours, and naturally airing the membrane to obtain the cobalt @ iron double-metal hydroxide doped mixed matrix ultrafiltration membrane.
Example 4
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
② mixing in the step I35mLCoCl is dripped into the mixed solution2And FeCl3The mixed aqueous solution of (1), CoCl of the mixed aqueous solution2And FeCl3The concentration is respectively 0.2mol/L and 0.4mol/L, and the mixture is stirred for 15 minutes to obtain the Co-containing material2+And Fe3+The reverse micelle microemulsion of (1).
And thirdly, 9mL of ammonia water with the concentration of 7mol/L is dripped into the reverse micelle microemulsion prepared in the second step, and the mixture is stirred for 0.5 hour to prepare the reverse micelle microemulsion containing the cobalt @ iron double-metal hydroxide nano particles.
Mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 950g of polyvinylidene fluoride solution with 50g of reverse micelle microemulsion prepared in the third step, and stirring at 60 ℃ for 6 hours to obtain the membrane casting solution.
Fifthly, standing and defoaming the casting solution prepared in the step IV, uniformly coating the casting solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, rapidly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a membrane, transferring the membrane to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the membrane after soaking for 24 hours, and naturally airing the membrane to obtain the cobalt @ iron double-metal hydroxide doped mixed matrix ultrafiltration membrane.
Example 5
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
② dripping 35mLCoCl into the mixed liquid prepared in the step I2And FeCl3The mixed aqueous solution of (1), CoCl of the mixed aqueous solution2And FeCl3The concentration is respectively 0.2mol/L and 0.4mol/L, and the mixture is stirred for 15 minutes to obtain the Co-containing material2+And Fe3+The reverse micelle microemulsion of (1).
And thirdly, 9mL of ammonia water with the concentration of 7mol/L is dripped into the reverse micelle microemulsion prepared in the second step, and the mixture is stirred for 0.5 hour to prepare the reverse micelle microemulsion containing the cobalt @ iron double-metal hydroxide nano particles.
Mixing 200g of polyvinylidene fluoride, 45g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 850g of polyvinylidene fluoride solution with 150g of reverse micelle microemulsion prepared in the third step, and stirring for 6 hours at 60 ℃ to obtain the membrane casting solution.
Fifthly, standing and defoaming the casting solution prepared in the step IV, uniformly coating the casting solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, rapidly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a membrane, transferring the membrane to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the membrane after soaking for 24 hours, and naturally airing the membrane to obtain the cobalt @ iron double-metal hydroxide doped mixed matrix ultrafiltration membrane.
Comparative example 1
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
And secondly, dropping 44mL of water into the mixed solution prepared in the step I, and stirring for 15 minutes to prepare the reverse micelle microemulsion.
③ mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 950g of polyvinylidene fluoride solution with 50g of reverse micelle microemulsion prepared in the third step, and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Standing and defoaming the polymer solution prepared in the step (III), uniformly coating the polymer solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, quickly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a film, transferring the film to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the film after soaking for 24 hours, and naturally airing the film to obtain the ultrafiltration membrane.
Comparative example 2
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
And secondly, dropping 44mL of water into the mixed solution prepared in the step I, and stirring for 15 minutes to prepare the reverse micelle microemulsion.
③ mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 900g of polyvinylidene fluoride solution with 100g of reverse micelle microemulsion prepared in the step (c), and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Standing and defoaming the polymer solution prepared in the step (III), uniformly coating the polymer solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, quickly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a film, transferring the film to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the film after soaking for 24 hours, and naturally airing the film to obtain the ultrafiltration membrane.
Comparative example 3
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
And secondly, dropping 44mL of water into the mixed solution prepared in the step I, and stirring for 15 minutes to prepare the reverse micelle microemulsion.
③ mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 850g of polyvinylidene fluoride solution with 150g of reverse micelle microemulsion prepared in the third step, and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Standing and defoaming the polymer solution prepared in the step (III), uniformly coating the polymer solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, quickly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a film, transferring the film to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the film after soaking for 24 hours, and naturally airing the film to obtain the ultrafiltration membrane.
Comparative example 4
200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide are mixed and stirred to be dissolved to obtain a polyvinylidene fluoride solution.
And secondly, standing and defoaming the polyvinylidene fluoride solution prepared in the step I, uniformly coating the flat and clean glass plate (with the coating thickness of 200 microns), standing the glass plate coated with the casting solution in the air for 1 minute, quickly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a film, transferring the film to a container filled with a large amount of purified water (with the water temperature of 40 ℃) after 1 hour, taking out the film after soaking for 24 hours, and naturally airing the film to obtain the ultrafiltration membrane.
Comparative example 5
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
② dripping 35mLFeCl into the mixed liquid prepared in the step I3Solutions, FeCl3The concentration is 0.6mol/L, the mixture is stirred for 15 minutes, and the Fe-containing material is prepared3+The reverse micelle microemulsion of (1).
And thirdly, 9mL of ammonia water with the concentration of 7mol/L is dripped into the reverse micelle microemulsion prepared in the second step, and the mixture is stirred for 0.5 hour to prepare the reverse micelle microemulsion containing the cobalt @ iron double-metal hydroxide nano particles.
Mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 900g of polyvinylidene fluoride solution with 100g of reverse micelle microemulsion prepared in the step (c), and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Fifthly, standing and defoaming the casting solution prepared in the step IV, uniformly coating the casting solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, rapidly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a membrane, transferring the membrane to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the membrane after soaking for 24 hours, and naturally airing the membrane to obtain the iron-doped monometal hydroxide mixed matrix ultrafiltration membrane.
Comparative example 6
320mL of cyclohexane, 80mL of octylphenol polyoxyethylene ether and 40mL of n-butanol are mixed at 25 ℃ and stirred for 15 minutes to obtain a mixed solution.
② dripping 35mLCoCl into the mixed liquid prepared in the step I2Solution, CoCl2The concentration is 0.6mol/L,stirring for 15 minutes to obtain a mixture containing Co2+The reverse micelle microemulsion of (1).
And thirdly, 9mL of ammonia water with the concentration of 7mol/L is dripped into the reverse micelle microemulsion prepared in the second step, and the mixture is stirred for 0.5 hour to prepare the reverse micelle microemulsion containing the cobalt @ iron double-metal hydroxide nano particles.
Mixing 200g of polyvinylidene fluoride, 40g of polyethylene glycol (molecular weight 2000) and 1000mL of N, N' -dimethylacetamide, and stirring for dissolving to obtain a polyvinylidene fluoride solution; and (3) mixing 900g of polyvinylidene fluoride solution with 100g of reverse micelle microemulsion prepared in the step (c), and stirring at 60 ℃ for 6 hours to prepare the membrane casting solution.
Fifthly, standing and defoaming the casting solution prepared in the step IV, uniformly coating the casting solution on a flat and clean glass plate (the coating thickness is 200 mu m), standing the glass plate coated with the casting solution in the air for 1 minute, rapidly immersing the glass plate in purified water at 25 ℃ for phase conversion to form a membrane, transferring the membrane to a container filled with a large amount of purified water (the water temperature is 40 ℃) after 1 hour, taking out the membrane after soaking for 24 hours, and naturally airing the membrane to obtain the cobalt-doped monometal hydroxide mixed matrix ultrafiltration membrane.
Pure water flux and anti-pollution performance of the above example and comparative example membranes were tested and evaluated:
the ultrafiltration membranes of examples 1-5 and comparative examples 1-4 were tested and evaluated for performance by dead-end filtration using pure water and 1g/L aqueous solution of bovine serum albumin as filtration media.
Test testing and evaluation procedures and methods: firstly, filling an ultrafiltration membrane into an ultrafiltration cup at 25 ℃, and prepressing for 30 minutes under the pressure of 0.15 MPa; ② the initial pure water flux J of the ultrafiltration membrane is measured by using pure water as filtering mediumwTesting for 30 minutes under the pressure of 0.1 MPa; thirdly, replacing the filtering medium with 1g/L bovine serum albumin aqueous solution, carrying out ultrafiltration treatment for 30 minutes under 0.1MPa, measuring the concentration of bovine serum albumin in the permeation solution, and calculating the retention rate R of the membrane to the bovine serum albumin; taking the ultrafiltration membrane out of the ultrafiltration cup, and washing the polluted ultrafiltration membrane for 15 minutes by using pure water; fifthly, the cleaned ultrafiltration membrane is put into an ultrafiltration cup, prepressed for 30 minutes under the pressure of 0.15MPa, and then the pure water flux (recovery flux) J of the ultrafiltration membrane is measured under the pressure of 0.1MParAnd is pure from the originalWater flux JwBy contrast, pure water flux recovery (FRR) was obtained.
Separation Performance of Ultrafiltration Membrane initial pure Water flux JwThe retention rate R of bovine serum albumin was evaluated, and the anti-contamination performance was evaluated by the pure water Flux Recovery Rate (FRR) of the membrane.
Wherein: c0Initial bovine serum albumin concentration (g/L), C1The concentration of bovine serum albumin in the filtrate (g/L) was used.
Prepared ultrafiltration membrane of formula JwThe larger R and FRR are, the better the separation performance and the anti-pollution performance of the membrane are.
The results of the separation performance and anti-pollution performance test of the membranes of examples 1-5 and comparative examples 1-4 are shown in Table 1.
Table 1 film performance test results
Example 1, example 2, and example 3 represent the dropwise addition of Co to the formation of reverse micelle microemulsions containing cobalt @ iron double hydroxide nanoparticles2+、Fe3+And mixing the cobalt @ iron double-metal hydroxide doped mixed matrix ultrafiltration membranes prepared by mixing inorganic salt aqueous solutions with different volumes.
Examples 4 and 5 were prepared by blending the reverse micelle microemulsion containing the cobalt @ iron double hydroxide nanoparticles formed in example 2 with the PVDF solution, but the blend mass ratio of the reverse micelle microemulsion to the PVDF solution was different in the preparation of the mixed matrix ultrafiltration membranes corresponding to them.
The ultrafiltration membranes corresponding to comparative example 1, comparative example 2 and comparative example 3 are respectivelyThe preparation method is characterized in that reverse micelle microemulsion which does not contain cobalt @ iron double metal hydroxide nano particles is blended with PVDF polymer solution, namely Co in inorganic salt aqueous solution is dripped in the formation of the reverse micelle microemulsion2+、Fe3+The concentration of (3) was zero, the ammonia concentration in the dropwise added aqueous ammonia was zero, and the addition volumes of both were the same as in example 2.
The ultrafiltration membrane corresponding to comparative example 4 was prepared using a PVDF solution.
The ultrafiltration membranes corresponding to the comparative examples 5 and 6 are respectively prepared by blending reverse micelle microemulsion containing iron hydroxide nano particles or cobalt hydroxide with PVDF polymer solution, namely, 0.6mol/L of CoCl is dripped in the formation of the reverse micelle microemulsion2Or FeCl3The concentration of the aqueous solution and dropwise added aqueous ammonia was 7mol/L, and the dropwise addition volumes of both solutions were the same as those in example 2.
The data of example 1, example 2, example 3 show that by successive dropwise addition of Co to a reverse micelle microemulsion2+、Fe3 +The inorganic salt aqueous solution and the ammonia aqueous solution are mixed to form the reverse micelle microemulsion containing the cobalt @ iron double metal hydroxide nano particles, and the performance of the mixed matrix ultrafiltration membrane prepared by blending the reverse micelle microemulsion containing the cobalt @ iron double metal hydroxide nano particles with the PVDF solution is obviously improved compared with that of ultrafiltration membranes (comparative example 1, comparative example 2 and comparative example 3) and pure PVDF ultrafiltration membrane (comparative example 4) prepared by blending the reverse micelle microemulsion containing no cobalt @ iron double metal hydroxide nano particles with the PVDF solution. But with the dropwise addition of Co to the reverse micelle microemulsion2+、Fe3+The increase of the mole number increases the number of the cobalt @ iron bimetallic hydroxide nanoparticles formed in the reverse micelle microemulsion and increases the particle size. When the number of the cobalt @ iron bimetallic hydroxide nanoparticles is increased and the particle size is increased to a certain degree, the dispersibility of the cobalt @ iron bimetallic hydroxide nanoparticles in the prepared mixed matrix ultrafiltration membrane is influenced, and the performance of the membrane is reduced.
From the data of example 2, example 4, and example 5, it can be seen that as the blending mass ratio of the reverse micelle microemulsion containing cobalt @ iron double hydroxide nanoparticles to the PVDF solution increases, the performance of the prepared mixed matrix ultrafiltration membrane shows a tendency of increasing first and then decreasing.
The mixed matrix ultrafiltration membrane prepared by the invention has the pure water flux of 328 L.m as in example 2-2·h-1The FRR is 80.5, the bovine serum albumin retention rate can reach 91 percent, and the retention rate is respectively improved by 5.4 times, 1.4 times and 1.47 times compared with a pure PVDF ultrafiltration membrane (comparative example 4). Initial pure water flux (J) of cobalt and iron double hydroxide doped mixed matrix ultrafiltration membrane (example 2) versus cobalt and iron doped alone under the same preparation conditionsw) Recovering the flux (J)r) FRR and R are superior to the mixed matrix ultrafiltration membrane doped with cobalt or iron hydroxide alone (comparative example 5 and comparative example 6), and the doping of the cobalt and iron double metal hydroxide has a synergistic effect on the improvement of the performance of the mixed matrix ultrafiltration membrane.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A preparation method of a cobalt @ iron bimetallic hydroxide nanoparticle-doped mixed matrix ultrafiltration membrane is characterized by comprising the following steps of:
(1) mixing and stirring an oil phase medium, a surfactant and a cosurfactant to obtain a mixed solution A;
(2) dropwise adding Co-containing solution into the mixed solution A under stirring2+Inorganic salts and Fe3+Mixed aqueous solution of inorganic salt to form a mixed solution containing Co2+And Fe3+The reverse micelle microemulsion B of (1);
(3) dropwise adding ammonia water into the obtained reverse micelle microemulsion B under stirring to obtain a reverse micelle microemulsion C containing the cobalt @ iron double-metal hydroxide nano particles;
(4) mixing the reverse micelle microemulsion C with a polyvinylidene fluoride solution according to a ratio to obtain a casting solution D;
(5) and (3) preparing the cobalt @ iron double metal hydroxide doped mixed matrix ultrafiltration membrane by using the membrane casting solution D through an immersion precipitation phase conversion method.
2. The preparation method according to claim 1, wherein in the step (1), the oil phase medium is a naphthenic organic matter, the surfactant is an organic matter of alkylphenol polyoxyethylene ether, and the cosurfactant is an organic matter of alcohol; the volume ratio of the oil phase medium to the surfactant to the cosurfactant is (2-10): 1: (0.3 to 1).
3. The production method according to claim 1, wherein in the step (2): said Co-containing2+Inorganic salts and Fe3+Co in mixed aqueous solution of inorganic salts2+And Fe3+The concentration of the (A) is 0.2-0.4 mol/L and 0.2-0.4 mol/L respectively; containing Co2+Inorganic salts and Fe3+The mixing volume ratio of the mixed aqueous solution of the inorganic salt to the surfactant in the mixed solution A is 1 (1.5-5).
4. The preparation method according to claim 1, wherein in the step (3), the concentration of the ammonia water is 6-8 mol/L, and the mole number of the dropwise added ammonia and the Co in the reverse micelle microemulsion B2+And Fe3+The ratio of the total molar number (2 to 3) to 1.
5. The preparation method according to claim 1, wherein in the step (4), the polyvinylidene fluoride solution is prepared by mixing and dissolving polyvinylidene fluoride, polyethylene glycol and N, N' -dimethylacetamide according to the mass, mass and volume ratio of (150-250) g, (30-50) g: 1L; the mixing mass ratio of the reverse micelle microemulsion C to the polyvinylidene fluoride solution is 1 (5-20).
6. The cobalt @ iron double hydroxide doped mixed matrix ultrafiltration membrane prepared by the preparation method of any one of claims 1 to 5.
7. Use of a cobalt @ iron double hydroxide doped mixed matrix ultrafiltration membrane according to claim 6 in the field of membrane separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111142559.4A CN113813798B (en) | 2021-09-28 | 2021-09-28 | Mixed matrix ultrafiltration membrane doped with cobalt@iron double metal hydroxide nanoparticles and preparation method thereof |
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