CN112090296A - Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof - Google Patents
Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 133
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 57
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 39
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004140 cleaning Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 238000005266 casting Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000007790 scraping Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 238000000614 phase inversion technique Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 230000001112 coagulating effect Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 15
- 230000004907 flux Effects 0.000 abstract description 7
- 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 abstract description 6
- 108091003079 Bovine Serum Albumin Proteins 0.000 abstract description 6
- 229940098773 bovine serum albumin Drugs 0.000 abstract description 6
- 239000004021 humic acid Substances 0.000 abstract description 6
- 239000013535 sea water Substances 0.000 abstract description 4
- 238000010612 desalination reaction Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- -1 silver ions Chemical class 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000004941 mixed matrix membrane Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229910000161 silver phosphate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/02—Inorganic material
-
- 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
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- 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
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- 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
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
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Abstract
The invention discloses a self-cleaning flat plate type PVDF ultrafiltration membrane based on F-TiO2/Fe-g-C3N4 and a preparation method thereof, belonging to the technical field of membrane separation. Adding 9.0-19.0% (w/w) polyvinylidene fluoride (PVDF), 5.0-13.0% (w/w) pore-forming agent, 0.1-1.0% (w/w) F-TiO2/Fe-g-C3N4 and 67.0-85.9% (w/w) solvent into a three-neck round-bottom flask according to a certain sequence, stirring and dissolving at 40-90 ℃ for 5-12 hours until completely dissolving, standing and defoaming for 8-16 hours, and preparing a casting solution; and scraping the membrane on a clean glass plate by adopting a phase inversion method to prepare the self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane. The pure water flux of the ultrafiltration membrane prepared by the invention is more than or equal to 330L/m 2 hr & lt 0.1MPa, the bovine serum albumin rejection rate is more than or equal to 90.00 percent, the degradation removal rate of humic acid reaches about 90 percent (simulating the operation for 1 hour under visible light), and the ultrafiltration membrane has good pollution resistance and visible light catalytic performance. The product of the invention is particularly suitable for the water treatment of micro-polluted water sources, the pretreatment of chemical engineering, medicine and seawater desalination, the treatment and recycling of wastewater in the biological field, and the like.
Description
Technical Field
The invention belongs to the technical field of membranes, relates to a high-molecular mixed matrix ultrafiltration membrane and a preparation method thereof, and particularly relates to a membrane based on F-TiO2/Fe-g-C3N4The self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane and the preparation method.
Background
The shortage of water resources and the increasingly serious water pollution become bottlenecks that restrict social progress and economic development, and the development of new water sources and the resource utilization of waste sewage also become global common concerns. Since most of the water resources of the earth are seawater and a large amount of sewage and wastewater is generated in the process of production and living of human beings, the reclamation of sewage and the desalination of seawater quickly become one of the most promising solutions for meeting the demand of water resources. In recent years, membrane technology has been widely used in sewage reuse and seawater desalination.
A mixed matrix membrane, also called a hybrid membrane, is a membrane formed by chemically crosslinking or microscopically mixing organic and inorganic components, also called an organic-inorganic hybrid membrane, and has the advantages of corrosion resistance and heat resistance of an inorganic membrane, high separability and toughness of an organic membrane and the like, so that the mixed matrix membrane becomes one of hot spots for researching the modification of membrane materials. In recent years, scholars at home and abroad adopt a blending method or a sol-gel method to prepare a nano inorganic material/polymer hybrid ultrafiltration membrane responding to ultraviolet light, so that the nano inorganic material/polymer hybrid ultrafiltration membrane has the multiple functions of photocatalysis and membrane separation and has good development and application prospects; for example, Chinese patent ZL201410312781.8 adopts a nano inorganic material and a membrane material to be blended to prepare an ultra-filtration membrane responding to ultraviolet light, so that the ultra-filtration membrane has the degradation performance on organic pollutants under the catalysis of the ultraviolet light; the practical application of the ultraviolet light catalyst modified film is severely limited because the light energy of the ultraviolet light only accounts for less than 5% of the solar light energy. Therefore, the visible light catalytic ultrafiltration membrane is prepared by doping or coating the visible light catalyst, the pollution resistance of the ultrafiltration membrane is improved, the visible light catalytic activity of the ultrafiltration membrane is realized, the application range of the ultrafiltration membrane is expanded, and the method is a hotspot of ultrafiltration membrane research in recent years; the research team of the inventor of the King of the Living nations carries out the research of related ultrafiltration membranes and preparation methods based on visible light catalytic nano inorganic materials, but does not relate to the preparation of mixed matrix ultrafiltration membranes and preparation methods based on visible light catalytic nano inorganic composite materials.
Chinese patent CN104383821A adopts graphene oxide loaded magnetic particles @ TiO with core-shell structure2The modified separation membrane is prepared, and the separation membrane is considered to show good photocatalytic degradation performance and protein pollution resistance to bovine serum albumin serving as a target pollutant, but the separation performance and the visible light photocatalytic degradation performance of the prepared membrane are not clarified in the patent application, and the preparation process of the separation membrane is complex; at the same time, graphene oxideMagnetic particle @ TiO of load core-shell structure2The preparation method is complex and has high cost. Chinese patent CN104117291A adopts TiO2The polyvinylidene fluoride membrane is prepared by modifying the/C hybrid aerogel, the degradation rate of the prepared membrane to the active bright red X-3B under the irradiation of a xenon lamp (visible light) is only 13.96 percent, and the degradation rate of the prepared membrane to the active bright red X-3B under the irradiation of a mercury lamp (ultraviolet light) is 93.28 percent, so that the prepared membrane is still an ultra-filtration membrane responding to the ultraviolet light instead of a visible light catalytic ultra-filtration membrane. Chinese patent CN102989329A is prepared by mixing AgNO3、TiO2The ultra-filtration membrane is prepared by blending modification, and actually, AgNO is mainly utilized3The visible light catalytic activity of the composite material is high, the degradation rate is low (the photocatalytic performance characterization is carried out on the degradation rate of methylene blue by adopting illumination for 10 hours in the patent), and a separation membrane for separation and visible light catalysis cannot be prepared; chinese patent CN104383820A discloses Ag3PO4 /TiO2Composite (Ag)3PO4Deposition of nanoparticles to TiO2Surface) and polyvinylidene fluoride material are blended and modified to make the modified film have visible light catalytic antibacterial and antifouling performance, and the modified film is mainly deposited on TiO2Surface Ag3PO4Organic matters adsorbed in the application process of the particle degradation separation membrane are reduced, so that membrane pollution is reduced, and the particle degradation separation membrane is not used for preparing a separation membrane with separation and visible light catalytic performances; also, neither patent utilizes silver salts and TiO by a synergistic effect2By mere blending or deposition, using silver salts or silver salts with TiO2The respective catalytic activity and visible light catalytic efficiency are low. Chinese patent CN102895888A firstly prepares a titanium dioxide/polyvinylidene fluoride film, and then prepares a visible light responsive polyvinylidene fluoride film by adsorbing and reducing silver ions on the surface of the film, wherein the methylene blue degradation rate of the prepared film is 33-51% (visible light irradiation 100 mins); meanwhile, the preparation of the patent product can be finished by the steps of adsorbing silver ions, reducing the silver ions into silver simple substances, vacuum drying and the like after the preparation of the titanium dioxide/polyvinylidene fluoride film is finished, and the preparation process needs a darkroom, ultraviolet irradiation, vacuum drying and other conditions, so that the process is complex, and the preparation method is complexHigh preparation cost and large industrialization difficulty.
Graphite phase carbon nitride (g-C)3N4) The polymer semiconductor with a layered structure can greatly absorb visible light, has good visible light catalytic performance, high chemical stability and acid or alkali environment competes, and is one of novel catalysts with application prospects. However a single g-C3N4Only small part of visible light can be absorbed by itself, and the absorption of ultraviolet light is poor, so that the g-C alone3N4The photocatalytic activity of (a) is not high, which limits its practical use. TiO22Is also a photocatalytic material with excellent performance, relatively simple preparation, low price and wide research and application, and the non-metallic element F is doped to modify TiO2Optionally adding TiO2The absorption spectrum of (a) extends into the visible region; the doping modification of the metallic element Fe can obviously improve g-C3N4Photocatalytic activity of (1). Thus, F-TiO is added2And Fe-g-C3N4The two are compounded, so that the synergistic effect of the two can be fully exerted, and the visible light catalytic activity of the composite can be obviously improved. Therefore, F-TiO is added2/Fe-g-C3N4The preparation method is used for developing the visible light catalysis mixed matrix ultrafiltration membrane by blending with a high polymer material, and has certain significance for improving the membrane separation efficiency, widening the application field of the separation membrane, reducing the membrane pollution and realizing the self-cleaning function of the membrane.
The invention adopts composite F-TiO2And Fe-g-C3N4To fully play the synergistic effect of the two, further improve the visible light catalytic activity of the two, and adopt F-TiO2And Fe-g-C3N4The visible light catalytic characteristic of the macromolecular ultrafiltration membrane is improved, and the flat plate type mixed matrix ultrafiltration membrane with the self-cleaning function is prepared, and no relevant literature report is found at home and abroad.
Disclosure of Invention
The invention aims to provide a catalyst based on F-TiO2/Fe-g-C3N4The invention also aims to provide a preparation method of the flat plate type mixed matrix ultrafiltration membrane.
In order to achieve the purpose, the invention adopts the technical scheme that:
based on F-TiO2/Fe-g-C3N4The self-cleaning flat plate type PVDF ultrafiltration membrane consists of the following substances in percentage by mass: 9.0-19.0% (w/w) of polymer film material, 5.0-13.0% (w/w) of pore-foaming agent and F-TiO2/Fe-g-C3N4 0.1-1.0% (w/w), and 67.0-85.9% (w/w) of solvent;
the polymer film material is polyvinylidene fluoride (PVDF), and the content is 9.0-19.0% (w/w);
the pore-foaming agent is polyethylene glycol (PEG-400), and the content is 5.0-13.0% (w/w);
the F-TiO2/Fe-g-C3N4The content of the self-made visible light catalytic nano inorganic compound is 0.1-1.0% (w/w);
the solvent is N, N-dimethylacetamide (DMAc), and the content is 67.0-85.9% (w/w).
Based on F-TiO2/Fe-g-C3N4The preparation method of the self-cleaning flat plate type PVDF ultrafiltration membrane comprises the following steps:
(1) mixing a certain amount of solvent and F-TiO2/Fe-g-C3N4And a pore-foaming agent are respectively added into the three-mouth round-bottom flask according to a certain proportion and sequence, and are uniformly stirred;
(2) adding polyvinylidene fluoride into a three-neck round-bottom flask, stirring and dissolving at 40-90 ℃ for 5-12 hours until the polyvinylidene fluoride is completely dissolved, standing and defoaming for 8-16 hours to obtain a self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane solution;
(3) pouring the defoamed membrane casting solution on a clean glass plate, scraping the membrane casting solution into a membrane by using a special flat membrane scraper, standing the membrane in the air for 15-60 seconds, slightly putting the glass plate into a constant-temperature coagulating bath at 20-60 ℃ for coagulating and forming, automatically separating the membrane from the glass plate after forming, taking out the membrane, washing the membrane by using deionized water, and soaking the membrane in a mixed solution of 50% of glycerol and 0.5% of tween 80 to obtain the F-TiO-based membrane2/Fe-g-C3N4The self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane.
The coagulating bath is deionized water.
The invention provides a catalyst based on F-TiO2/Fe-g-C3N4The self-cleaning flat plate type PVDF ultrafiltration membrane is prepared by mixing visible light catalytic material F-TiO2/Fe-g-C3N4The composite is introduced into the polymer to prepare the mixed matrix ultrafiltration membrane, and the mixed matrix ultrafiltration membrane is endowed with good pollution resistance, organic pollutant degradation by visible light catalysis and self-cleaning performance, which is the innovation of the invention. In order to test the pollution resistance and the visible light catalysis performance of the prepared visible light catalysis mixed matrix ultrafiltration membrane, the resistance increase coefficient and the contact angle of the prepared ultrafiltration membrane are tested, and the result shows that the resistance increase coefficient and the contact angle are both obviously reduced, and the pollution resistance of the ultrafiltration membrane is greatly improved. Meanwhile, by taking humic acid as a target pollutant, the visible light catalytic degradation removal rate and ultrafiltration membrane flux change test are carried out on the prepared visible light catalytic mixed matrix ultrafiltration membrane, and the result shows that the prepared ultrafiltration membrane shows good photocatalytic degradation performance and pollution resistance performance when running under simulated visible light, and the flux attenuation of the membrane is obviously reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the F-TiO provided by the invention2/Fe-g-C3N4Compared with the traditional flat polyvinylidene fluoride ultrafiltration membrane, the self-cleaning flat mixed matrix ultrafiltration membrane prepared by blending modification has the advantages that the pollution resistance, the visible light catalytic activity and the self-cleaning performance are obviously improved, and the catalytic degradation of organic pollutants can be realized while the membrane separation is carried out.
(2) The F-TiO provided by the invention2/Fe-g-C3N4The method for preparing the self-cleaning flat plate type mixed matrix ultrafiltration membrane by blending modification has the advantages of simple and easily-controlled equipment and simple membrane preparation process, endows the prepared ultrafiltration membrane with visible light catalytic activity, pollution resistance and self-cleaning performance while forming the membrane, is convenient for large-scale industrial production, and is easy to realize industrialization.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
73.2% (w/w) of dimethylacetamide and 0.8% (w/w) of F-TiO2/Fe-g-C3N4And 11.0% (w/w) of polyethylene glycol 400 are respectively added into the three-neck round-bottom flask according to a certain sequence and stirred uniformly; then adding 15.0% (w/w) of polyvinylidene fluoride, stirring and dissolving for 8 hours at the temperature of 70 ℃ until the polyvinylidene fluoride is completely dissolved; then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 12 hours, and bubbles remaining in the casting solution were removed.
Pouring the defoamed membrane casting solution on a clean glass plate, scraping the membrane casting solution into a membrane by using a special flat membrane scraper, standing the membrane in the air for 30 seconds, immersing the membrane casting solution into a constant-temperature coagulating bath at 40 ℃ for coagulating and forming, automatically separating the membrane from the glass plate after the membrane forming, taking out the membrane, washing the membrane by using deionized water for 24 hours, and soaking the membrane in a mixed solution of 50% of glycerol and 0.5% of Tween 80 for 48 hours to obtain the F-TiO-based composite membrane2/Fe-g-C3N4The self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane.
The pure water flux of the self-cleaning flat plate type mixed matrix ultrafiltration membrane prepared by the embodiment is 336.97L/m2Hr.0.1 MPa, bovine serum albumin rejection 93.71%, resistance increase coefficient 1.23, contact angle 71.9 °; the degradation removal rate of humic acid is improved from 51.71% (without illumination and running for 1 hour) to 91.26% (under simulated visible light, running for 1 hour).
Example 2:
F-TiO is mixed with2/Fe-g-C3N4The content was reduced from 0.8% (w/w) to 0.1% (w/w), and the content of dimethylacetamide was increased from 73.2% (w/w) to 73.9% (w/w), the rest being the same as in example 1. The prepared F-TiO-based2/Fe-g-C3N4The pure water flux of the self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane is 285.61L/m2Hr.0.1 MPa, bovine serum albumin rejection 95.03%, resistance increase coefficient 1.63, contact angle 80.9 °; the degradation removal rate of humic acid is improved from 32.31 percent (without light and running for 1 hour) to 44.16% (simulated visible light, run for 1 hour).
Example 3:
F-TiO is mixed with2/Fe-g-C3N4The content was increased from 0.8% (w/w) to 1.0% (w/w), and the content of dimethylethylamine was decreased from 73.2% (w/w) to 73.0% (w/w), the rest being the same as in example 1. The prepared F-TiO-based2/Fe-g-C3N4The pure water flux of the self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane is 319.22L/m2Hr.0.1 MPa, bovine serum albumin rejection 90.59%, resistance increase coefficient 1.22, contact angle 71.6 °; the degradation removal rate of humic acid is improved from 51.86% (without illumination and running for 1 hour) to 91.39% (under simulated visible light, running for 1 hour).
Comparative example 1:
respectively adding 74.0% (w/w) of dimethylacetamide, 11.0% (w/w) of polyethylene glycol 400 and 15.0% (w/w) of polyvinylidene fluoride into a three-neck round-bottom flask according to a certain sequence, and stirring and dissolving at the temperature of 70 ℃ for 8 hours until the materials are completely dissolved; then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 12 hours, and bubbles remaining in the casting solution were removed.
Pouring the defoamed membrane casting solution on a clean glass plate, scraping the membrane casting solution into a membrane by using a special flat membrane scraper, standing in the air for 30 seconds, immersing the membrane casting solution into a constant-temperature coagulating bath at 40 ℃ for coagulating and forming, automatically separating the membrane from the glass plate after the membrane forming, taking out the membrane, washing the membrane by using deionized water for 24 hours, and soaking the membrane in a mixed solution of 50% of glycerol and 0.5% of Tween 80 for 48 hours to obtain the flat PVDF ultrafiltration membrane.
The pure water flux of the flat plate type ultrafiltration membrane prepared in this comparative example was 265.13L/m2Hr · 0.1MPa, bovine serum albumin rejection of 92.19%, resistance increase coefficient of 1.71, contact angle of 83.5 °; the degradation removal rate of humic acid is improved from 29.67 percent (no light and operation for 1 hour) to 31.98 percent (operation for 1 hour under simulated visible light).
Claims (4)
1. A self-cleaning flat PVDF ultrafiltration membrane based on F-TiO2/Fe-g-C3N4 is characterized in that a membrane casting solution contains F-TiO2/Fe-g-C3N4 and influences the structure and performance of a mixed matrix ultrafiltration membrane; the casting solution consists of the following substances in percentage by mass: 9.0-19.0% (w/w) of polymer film material, 5.0-13.0% (w/w) of pore-forming agent, F-TiO 2/Fe-g-C3N40.1-1.0% (w/w) and the balance of solvent;
the polymer film material is polyvinylidene fluoride (PVDF); the pore-foaming agent is polyethylene glycol (PEG-400); the F-TiO2/Fe-g-C3N4 is a self-made visible light catalytic nano inorganic compound; the solvent is N, N-dimethylacetamide (DMAc).
2. The F-TiO2/Fe-g-C3N 4-based self-cleaning flat plate type PVDF ultrafiltration membrane of claim 1, wherein the ultrafiltration membrane is prepared by a conventional phase inversion method, namely a dry-wet method.
3. A method for preparing the F-TiO2/Fe-g-C3N 4-based self-cleaning flat PVDF ultrafiltration membrane of claim 1 or 2, which is characterized by comprising the following steps:
step (1), adding a certain amount of solvent, F-TiO2/Fe-g-C3N4 and a pore-foaming agent into a three-neck round-bottom flask according to a certain proportion and sequence, and uniformly stirring;
adding polyvinylidene fluoride into a three-neck round-bottom flask, stirring and dissolving at 40-90 ℃ for 5-12 hours until the polyvinylidene fluoride is completely dissolved, standing and defoaming for 8-16 hours to obtain a self-cleaning flat plate type PVDF mixed matrix ultrafiltration membrane solution;
and (3) pouring the defoamed membrane casting solution on a clean glass plate, scraping the membrane casting solution into a membrane by using a special flat membrane scraper, standing the membrane in the air for 15-60 seconds, slightly putting the glass plate into a constant-temperature coagulating bath at 20-60 ℃ for coagulating and forming, automatically separating the formed membrane from the glass plate, taking out the membrane, washing the membrane by using deionized water, and soaking the membrane in a mixed solution of 50% of glycerol and 0.5% of tween 80 to obtain the F-TiO2/Fe-g-C3N 4-based self-cleaning flat PVDF mixed matrix ultrafiltration membrane.
4. The method for preparing the F-TiO2/Fe-g-C3N 4-based self-cleaning flat plate type PVDF ultrafiltration membrane as claimed in claim 3, wherein the coagulation bath is deionized water.
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