CN112121648A - Polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance and preparation method and application thereof - Google Patents
Polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance and preparation method and application thereof Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 87
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 86
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 23
- 238000004140 cleaning Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 122
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002114 nanocomposite Substances 0.000 claims abstract description 33
- 238000005266 casting Methods 0.000 claims abstract description 26
- 238000005191 phase separation Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000000108 ultra-filtration Methods 0.000 description 19
- 239000011941 photocatalyst Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 239000005591 Pendimethalin Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- CHIFOSRWCNZCFN-UHFFFAOYSA-N pendimethalin Chemical compound CCC(CC)NC1=C([N+]([O-])=O)C=C(C)C(C)=C1[N+]([O-])=O CHIFOSRWCNZCFN-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000007790 scraping Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 oxygen free radical Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910018292 Cu2In Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
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- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Images
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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
-
- 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
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- 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
- 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
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/34—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- 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
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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 relates to a polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance, a preparation method and application thereof, wherein the preparation method comprises the following steps: SnO2‑Cu2Mixing the O nano composite material with polyvinylidene fluoride, preparing to obtain a membrane casting solution, and then preparing a polyvinylidene fluoride mixed matrix membrane by a non-solvent induced phase separation method; the mixed matrix membrane can be used for improving the organic pollutant resistance of a catalytic membrane reactor device. Compared with the prior art, the invention uses SnO2‑Cu2O is added into the polyvinylidene fluoride casting solution in the form of additive, and the PVDF membrane is modified by introducing inorganic nano particle blending method and NIPS method, so that the composite material is formedThe membrane has improved mechanical strength, greatly enhanced hydrophilicity, and better anti-pollution capability and interception performance.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and relates to a polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance, and a preparation method and application thereof.
Background
The membrane separation technology is one of the preferable technologies in the field of water pollution control engineering, and is widely applied to drinking water purification and sewage and wastewater treatment and reutilization due to low cost, good effluent quality, high intensification degree, simple equipment and convenient operation. However, the membrane pollution phenomenon, especially organic pollution, often causes the attenuation of membrane flux, the increase of operation cost and the shortening of membrane service life, thereby becoming a major obstacle for the wide application of membrane separation technology in drinking water, sewage and wastewater treatment.
Polyvinylidene fluoride (PVDF) is a vinylidene fluoride homopolymer or a copolymer of vinylidene fluoride and other small amount of fluorine-containing vinyl monomers, has the characteristics of good chemical corrosion resistance, high temperature resistance, radiation resistance, easy film formation and the like, and is widely applied to various water treatment fields such as domestic sewage treatment, industrial wastewater treatment and the like as a typical ultrafiltration membrane material. However, the surface energy of the PVDF membrane material is low, the affinity with water is poor, and hydrophobic organic pollutants such as proteins or oils are easily adsorbed to the surface of the membrane to cause membrane pollution, so that the economy and reliability of the membrane are affected, and the development, application and popularization of the PVDF membrane material are restricted. It is known that the pollution resistance of PVDF membranes can be improved by physical and chemical means, and the modification methods can be largely classified into membrane surface modification and membrane material modification. The modification of the membrane material can be divided into chemical modification and blending modification of the membrane material, and the latter is convenient for large-scale popularization due to simple operation and difficult falling of hydrophilic groups, and is a hotspot of research in recent years.
The photocatalysis technology is a emerging, high-efficiency and environment-friendly technical means in the field of water treatment in recent years, and the technology utilizes renewable light energy to generate active groups to degrade organic pollutants in water. Therefore, the photocatalysis technology is combined with the membrane modification technology to form the composite photocatalysis separation modified membrane, and the self-cleaning capability, the hydrophilic performance and the interception characteristic of the membrane can be effectively improved. The technology of coupling photocatalysis and membrane separation is gradually applied to membrane separation research, and Chinese patent CN103881122B discloses a preparation method of a polyvinyl chloride/nano tin dioxide composite membrane with high visible light catalytic activity. However, the membrane prepared by the method has insufficient pollution resistance to organic pollutant pendimethalin and low interception efficiency.
Disclosure of Invention
The invention aims to provide a polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance, a preparation method and application thereof, which are used for solving the problem of membrane pollution of a polyvinylidene fluoride membrane.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a polyvinylidene fluoride (PVDF) mixed matrix membrane with photocatalytic self-cleaning performance comprises the following steps: SnO2-Cu2Mixing the O nano composite material with polyvinylidene fluoride, preparing to obtain a casting solution, and then preparing the polyvinylidene fluoride mixed matrix membrane by a non-solvent induced phase separation method (NIPS).
Further, said SnO2-Cu2The preparation method of the O nanocomposite comprises the following steps: preparing a mixed solution from copper salt, tin salt and hydrochloric acid, adjusting the pH value to 7-12, adding a reducing agent, reacting at room temperature, and sequentially centrifuging, washing, drying and calcining the obtained product to obtain the SnO2-Cu2An O nanocomposite.
Further, the copper salt comprises cuprous chloride, and the tin salt comprises stannous chloride;
the molar ratio of the copper salt to the tin salt is (1-4) to (0.1-2);
the addition amount of the hydrochloric acid is 10-30mL/mol Cu, and the concentration of the hydrochloric acid is 30-40 mol/L;
the preparation method of the mixed solution comprises the following steps: adding copper salt, tin salt and hydrochloric acid into deionized water, and performing ultrasonic treatment for 15-45 min;
the reducing agent comprises hydrazine hydrate, and the addition amount of the hydrazine hydrate is 10-30mL/mol Cu;
in the reduction reaction, the reaction time is 1-4 h.
Further, in the washing process, the detergent is ethanol;
the drying process comprises vacuum drying at 40-80 deg.C;
in the calcining process, the calcining atmosphere comprises argon, the calcining temperature is 100-400 ℃, and the calcining time is 1-4 h.
Further, the preparation method of the casting solution comprises the following steps: SnO2-Cu2Adding the O nano composite material, the pore-foaming agent and the polyvinylidene fluoride into N, N-dimethylformamide, uniformly stirring, standing and defoaming to obtain the casting solution.
Further, the pore-foaming agent comprises polyvinylpyrrolidone;
said SnO2-Cu2The mass ratio of the O nano composite material, the pore-forming agent and the polyvinylidene fluoride is (0.1-1.6) to 1 (14-20);
in the stirring process, the stirring temperature is 30-80 ℃, and the stirring time is 8-18 h;
and in the standing and defoaming process, the standing time is 5-12 h.
Further, the non-solvent induced phase separation method comprises: and (3) coating the casting solution on a substrate in a blade mode, and placing the substrate in a gel bath for phase separation to obtain the polyvinylidene fluoride mixed matrix membrane.
Further, the thickness of the scratch film is 100-260 μm;
the gel bath comprises a mixed solution of ethanol and water in a volume ratio of (0.5-1.5) to (0.8-1.3), and the temperature of the gel bath is 14-30 ℃.
The polyvinylidene fluoride mixed matrix membrane with the photocatalytic self-cleaning performance is prepared by the method, can be used for resisting organic pollutants, and is particularly used for improving the organic pollutant resistance of a catalytic membrane reactor device.
SnO of the present invention2-Cu2The PVDF ultrafiltration membrane modified by the O photocatalyst can be used for catalyzing a membrane reactor device, and organic pollutants on the surface of the membrane can be degraded under the irradiation of a visible light lamp, so that the membrane pollution phenomenon can be inhibited. Use of the SnO of the present invention2-Cu2The method for realizing the pollution resistance of the PVDF ultrafiltration membrane modified by the O photocatalyst under the irradiation of visible light comprises the following steps:
constructing a catalytic membrane reactor device to remove the contaminated SnO2-Cu2Fixing PVDF ultrafiltration membrane modified by O photocatalyst on membrane component, fixing LED visible light lamp on membrane surface, and carrying out photocatalysis for 30min2-Cu2The PVDF ultrafiltration membrane modified by the O photocatalyst is continuously used for a water flux experiment, so that organic matter pollution resistance is realized under the irradiation of an LED visible light lamp, and flux recovery is enhanced. The organic contaminants include pendimethalin.
SnO of the present invention2-Cu2O photocatalyst modified PVDF ultrafiltration membrane can activate SnO on membrane surface under irradiation of visible light2-Cu2The O photocatalyst generates active oxygen free radical with oxidability, and the active oxygen free radical can generate degradation reaction with organic pollutant to mineralize the pollutant into CO2And H2O。
When the polyvinylidene fluoride mixed matrix membrane is used for treating a pendimethalin solution, the membrane shows excellent pollution resistance, and the rejection rate is obviously improved. This is because the inorganic nanomaterial is embedded into the concave surface of the hybrid membrane surface during the phase separation process, which results in a smoother membrane surface that is less prone to contaminant accumulation. On the other hand, as hydrophilicity increases, the "hydrated layer" of the membrane surface effectively prevents the access of foulants, making fouling accumulation in the membrane pores more difficult and exhibiting higher anti-fouling performance. Meanwhile, due to the fact that the modified membrane has a complex structure with uniform sponge pores and the pore diameter smaller than that of pendimethalin molecules, pendimethalin molecules can be effectively intercepted, and high rejection rate is shown.
The preparation method of the invention is to prepare the prepared SnO2-Cu2The polyvinylidene fluoride casting solution is added into the O in the form of an additive, and the PVDF membrane is modified by introducing an inorganic nanoparticle blending method and an NIPS method, so that the mechanical strength of the composite membrane is improved, the hydrophilicity of the composite membrane is greatly improved, the composite membrane has better anti-pollution capacity and interception performance, and the blending is the simplest and the most common membrane modification method. Compared with other methods, the blending modification has the following advantages: the modification and the film formation are carried out synchronously, the process is simple, and complicated post-treatment steps are not needed; the additive can cover the membrane surface and the inner wall of the membrane hole at the same time and can not cause the damage of the membrane structure.
Compared with the prior art, the invention has the following characteristics:
1) SnO provided by the invention2-Cu2Compared with the traditional PVDF ultrafiltration membrane, the PVDF ultrafiltration membrane modified by the O photocatalyst has higher hydrophilicity and remarkable photocatalytic performance; SnO2-Cu2In O photocatalyst, Cu2O and SnO2The combination of the two can form a heterojunction structure, improve the optical response performance of the two and avoid SnO2Photo-corrosion phenomenon of2The addition of O improves the electron transmission rate and effectively promotes SnO2-Cu2The visible light response capability of O has good anti-pollution effect under the irradiation of visible light, and can effectively reduce the membrane pollution phenomenon and slow down the reduction rate of the membrane flux;
2) SnO provided by the invention2-Cu2PVDF ultrafiltration membrane modified by O photocatalyst and ultraviolet photocatalyst (such as TiO)2) Compared with the modified PVDF membrane, the energy consumption and the cost are obviously reduced;
3) SnO prepared by the invention2-Cu2The method for modifying the PVDF ultrafiltration membrane by the O photocatalyst is simple and easy to operate, the used equipment is conventional instruments in the field, the process period is short, the requirement on the process environment is low, the cost is low, and the method can be widely applied to the photocatalysisPreparing a chemical agent modified PVDF membrane;
4) SnO prepared by the invention2-Cu2The method for modifying PVDF ultrafiltration membrane by O photocatalyst is a blending modification method, and the photocatalyst SnO in the modified membrane2-Cu2O is not easy to dissolve out along with water flow in the using process, thereby avoiding poisoning and potential secondary pollution to the water body and ensuring the durability and stability of the membrane structure.
Drawings
FIG. 1 is a SnO prepared in example 12-Cu2Scanning electron micrographs of O particles;
FIG. 2 is a scanning electron micrograph of a cross section of a uniform polyvinylidene fluoride film prepared in example 4;
FIG. 3 shows SnO prepared in examples 4 to 82-Cu2A curve of the change of the water flux of the PVDF membrane (M4-M8) modified by the O photocatalyst and the PVDF original membrane M0 with time when the PVDF original membrane is irradiated by visible light;
FIG. 4 is a SnO prepared in examples 4-82-Cu2The water flux and the retention rate of the PVDF membrane (M4-M8) modified by the O photocatalyst are compared with those of the PVDF original membrane M0.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A preparation method of a polyvinylidene fluoride (PVDF) mixed matrix membrane with photocatalytic self-cleaning performance comprises the following steps:
1)SnO2-Cu2preparing an O nano composite material: cuprous chloride (CuCl)2) Stannous chloride dihydrate (SnCl)2·2H2O) and hydrochloric acid are added into deionized water, the mixture is subjected to ultrasonic treatment for 15-45min to obtain a mixed solution, the pH value of the mixed solution is adjusted to 7-12, a reducing agent hydrazine hydrate is added, the mixture reacts for 1-4h at room temperature, the obtained product is subjected to centrifugal separation, precipitate is taken and washed by ethanol, the precipitate is subjected to vacuum drying at the temperature of 40-80 ℃, and finally the precipitate is calcined for 1-4h at the temperature of 100-400 ℃ in the argon atmosphere to obtain SnO2-Cu2An O nanocomposite;
wherein, CuCl2With SnCl2·2H2The molar ratio of O is (1-4) to (0.1-2); the addition amount of the hydrochloric acid is 10-30mL/mol Cu, and the concentration of the hydrochloric acid is 30-40 mol/L; the adding amount of hydrazine hydrate is 10-30mL/mol Cu;
2) preparing a casting solution: SnO2-Cu2Adding an O nano composite material, a pore-forming agent polyvinylpyrrolidone (PVP) and polyvinylidene fluoride (PVDF) into N, N-Dimethylformamide (DMF), stirring for 8-18h at 30-80 ℃, standing and defoaming to obtain a membrane casting solution;
wherein SnO2-Cu2The mass ratio of the O nano composite material, the pore-forming agent and the polyvinylidene fluoride is (0.1-1.6) to 1 (14-20);
3) preparing a polyvinylidene fluoride mixed matrix membrane by a non-solvent induced phase separation method: and (3) coating the casting solution on a glass plate in a scraping thickness of 260 mu m and placing the glass plate in a gel bath at 14-30 ℃ consisting of ethanol and water in a volume ratio of (0.5-1.5) to (0.8-1.3) for phase separation to obtain the polyvinylidene fluoride mixed matrix membrane.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1:
this example is for the preparation of SnO2-Cu2The preparation method of the O nano composite material comprises the following steps:
1) 0.01mol of CuCl2、0.005mol SnCl2·2H2Adding O and 0.2mL of 35mol/L hydrochloric acid into 200mL of deionized water, and carrying out ultrasonic treatment for 30min to obtain a mixed solution;
2) adding ammonia water into the mixed solution until the pH value of the solution is 9.0, then adding 0.2mL of hydrazine hydrate, and carrying out reduction reaction for 2h at room temperature;
3) washing the obtained product with ethanol, vacuum drying at 60 deg.C, and calcining the dried powder at 200 deg.C under protection of argon gas for 2 hr to obtain SnO2-Cu2An O nanocomposite.
For the resultant SnO2-Cu2The O nanocomposite was subjected to scanning electron microscopy characterization, and the results are shown in FIG. 1.
Example 2:
this example is for the preparation of SnO2-Cu2The preparation method of the O nano composite material comprises the following steps:
1) 0.04mol of CuCl2、0.004mol SnCl2·2H2Adding O and 0.4mL of 30mol/L hydrochloric acid into 200mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
2) adding ammonia water to the mixed solution until the pH value of the solution is 9.0, then adding 0.4mL of hydrazine hydrate, and carrying out reduction reaction for 1h at room temperature;
3) washing the obtained product with ethanol, vacuum drying at 40 deg.C, and calcining the dried powder at 100 deg.C for 1h under protection of argon to obtain SnO2-Cu2An O nanocomposite.
Example 3:
this example is for the preparation of SnO2-Cu2The preparation method of the O nano composite material comprises the following steps:
1) 0.07mol of CuCl2、0.035mol SnCl2·2H2Adding O and 2.1mL of 40mol/L hydrochloric acid into 200mL of deionized water, and carrying out ultrasonic treatment for 45min to obtain a mixed solution;
2) adding ammonia water to the mixed solution until the pH value of the solution is 9.0, then adding 2.1mL of hydrazine hydrate, and carrying out reduction reaction for 4h at room temperature;
3) washing the obtained product with ethanol, vacuum drying at 80 deg.C, and calcining the dried powder at 400 deg.C under protection of argon for 4 hr to obtain SnO2-Cu2An O nanocomposite.
Example 4:
this example uses SnO from example 12-Cu2The preparation method of the polyvinylidene fluoride mixed matrix membrane further prepared from the O nano composite material comprises the following steps:
1) SnO2-Cu2Dissolving an O nano composite material, PVP and PVDF in DMF at a mass ratio of 0.3:1:15, stirring for 10 hours at 60 ℃ until the materials are fully dissolved, and standing and defoaming for 6 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 250 mu m;
3) immersing a glass plate with membrane liquid into a mixture of ethanol and deionized water at 15 ℃ in a volume ratio of 1.0:1.2 for phase separation;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a polyvinylidene fluoride mixed matrix membrane, which is marked as an M4 ultrafiltration membrane.
The obtained M4 ultrafiltration membrane was characterized by scanning electron microscopy, and the results are shown in fig. 2. As can be seen from the figure, the membrane cross-section is dense in surface but has large membrane pores.
Example 5:
this example uses SnO from example 12-Cu2The preparation method of the polyvinylidene fluoride mixed matrix membrane further prepared from the O nano composite material comprises the following steps:
1) SnO2-Cu2Dissolving an O nano composite material, PVP and PVDF in DMF at a mass ratio of 0.8:1:15, stirring for 10 hours at 70 ℃ until the materials are fully dissolved, and standing and defoaming for 10 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 150 mu m;
3) immersing a glass plate with the membrane liquid into a mixture of ethanol and deionized water at the temperature of 20 ℃ in a volume ratio of 0.8:1.0 to carry out phase separation;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a polyvinylidene fluoride mixed matrix membrane, which is marked as an M5 ultrafiltration membrane.
Example 6:
this example uses SnO from example 12-Cu2The preparation method of the polyvinylidene fluoride mixed matrix membrane further prepared from the O nano composite material comprises the following steps:
1) SnO2-Cu2Dissolving an O nano composite material, PVP and PVDF in DMF at a mass ratio of 1.5:1:15, stirring at 50 ℃ for 10 hours until the materials are fully dissolved, and standing and defoaming for 8 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 130 mu m;
3) immersing a glass plate with membrane liquid into a mixture of ethanol and deionized water at 25 ℃ in a volume ratio of 1.2:1.0 to perform phase separation;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a polyvinylidene fluoride mixed matrix membrane, which is marked as an M6 ultrafiltration membrane.
Example 7:
this example uses SnO from example 12-Cu2The preparation method of the polyvinylidene fluoride mixed matrix membrane further prepared from the O nano composite material comprises the following steps:
1) SnO2-Cu2Dissolving an O nano composite material, PVP and PVDF in DMF at a mass ratio of 0.1:1:14, stirring for 8 hours at 30 ℃ until the materials are fully dissolved, and standing and defoaming for 5 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 100 mu m;
3) immersing a glass plate with the membrane liquid into a mixture of ethanol and deionized water at 14 ℃ in a volume ratio of 0.5:0.8 for phase separation;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a polyvinylidene fluoride mixed matrix membrane, which is marked as an M7 ultrafiltration membrane.
Example 8:
this example uses SnO from example 12-Cu2The preparation method of the polyvinylidene fluoride mixed matrix membrane further prepared from the O nano composite material comprises the following steps:
1) SnO2-Cu2Dissolving an O nano composite material, PVP and PVDF in DMF at a mass ratio of 1.6:1:20, stirring at 80 ℃ for 18 hours until the materials are fully dissolved, and standing and defoaming for 12 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 260 mu m;
3) immersing a glass plate with the membrane liquid into a mixture of ethanol and deionized water at the temperature of 30 ℃ in a volume ratio of 1.5:1.3 for phase separation;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a polyvinylidene fluoride mixed matrix membrane, which is marked as an M8 ultrafiltration membrane.
Comparative example:
this example uses the NIPS method to prepare a non-SnO alloy2-Cu2The polyvinylidene fluoride flat membrane of the O nano composite material is prepared by the following specific steps:
1) dissolving PVP and PVDF in DMF at a mass ratio of 1:15, stirring at 60 ℃ for 10 hours until the PVP and the PVDF are fully dissolved, and standing and defoaming for 6 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 250 mu m;
3) immersing a glass plate with membrane liquid into a mixture of ethanol and deionized water at 15 ℃ in a volume ratio of 1.0:1.2 for phase separation;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain an unmodified polyvinylidene fluoride flat membrane, which is marked as an M0 ultrafiltration membrane.
Example 9:
this example was used to test the water flux and pendimethalin rejection of the ultrafiltration membranes of examples 4-8 and comparative examples, wherein the water flux and pendimethalin rejection test methods are described in the following references: wang, Gui-E Chen, Hai-Link Wu, contamination of GO-Ag/PVDF/F127 modified membrane IPA conjugation base for catalytic reduction of 4-nitrophenol, Sep.purif.Technol.235(2020) 116143. The results of the tests are shown in fig. 3 and 4, respectively, from which it can be seen that each of the nanoparticle-added membranes exhibited superior permeability and better separation performance compared to the original PVDF membrane. The permeability increase may be due to the influence of two main factors: 1) the addition of nanoparticles will impart hydrophilicity to the membrane, thereby increasing the rate of water passage through the membrane; 2) the pore size and porosity of the modified membrane is enlarged compared to the original membrane, which undoubtedly favors permeability. The improvement in separation performance can be illustrated by three reasons: 1) the pore size of the membrane is smaller than the size of the contaminant; 2) the complex structure of the complete sponge hole formed by delayed phase separation can effectively intercept pendimethalin molecules; 3) the theory of increased hydrophilicity with an interfacial hydration layer is used to reduce the contact between the contaminants and the membrane surface, thereby preventing the contaminants from penetrating the modified membrane. Meanwhile, compared with a membrane which is simply cleaned by water, the pendimethalin attached to the membrane pores can be effectively catalytically decomposed after the membrane is exposed to visible light, so that higher flux recovery rate is brought.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance is characterized by comprising the following steps: SnO2-Cu2Mixing the O nano composite material with polyvinylidene fluoride, preparing to obtain a membrane casting solution, and then preparing the polyvinylidene fluoride mixed matrix membrane by a non-solvent induced phase separation method.
2. The method for preparing polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance as claimed in claim 1, wherein said SnO2-Cu2The preparation method of the O nanocomposite comprises the following steps: preparing a mixed solution from copper salt, tin salt and hydrochloric acid, adjusting the pH value to 7-12, adding a reducing agent, reacting at room temperature, and sequentially centrifuging, washing, drying and calcining the obtained product to obtain the SnO2-Cu2An O nanocomposite.
3. The method for preparing polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance as claimed in claim 2, wherein the copper salt comprises cuprous chloride, and the tin salt comprises stannous chloride;
the molar ratio of the copper salt to the tin salt is (1-4) to (0.1-2);
the addition amount of the hydrochloric acid is 10-30mL/mol Cu, and the concentration of the hydrochloric acid is 30-40 mol/L;
the preparation method of the mixed solution comprises the following steps: adding copper salt, tin salt and hydrochloric acid into deionized water, and performing ultrasonic treatment for 15-45 min;
the reducing agent comprises hydrazine hydrate, and the addition amount of the hydrazine hydrate is 10-30mL/mol Cu;
in the reduction reaction, the reaction time is 1-4 h.
4. The method for preparing polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance as claimed in claim 2, wherein in the washing process, the detergent is ethanol;
the drying process comprises vacuum drying at 40-80 deg.C;
in the calcining process, the calcining atmosphere comprises argon, the calcining temperature is 100-400 ℃, and the calcining time is 1-4 h.
5. The preparation method of the polyvinylidene fluoride mixed matrix membrane with the photocatalytic self-cleaning performance as claimed in claim 1, wherein the preparation method of the membrane casting solution comprises the following steps: SnO2-Cu2Adding the O nano composite material, the pore-foaming agent and the polyvinylidene fluoride into N, N-dimethylformamide, uniformly stirring, standing and defoaming to obtain the casting solution.
6. The method for preparing polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance as claimed in claim 5, wherein the pore-forming agent comprises polyvinylpyrrolidone;
said SnO2-Cu2The mass ratio of the O nano composite material, the pore-forming agent and the polyvinylidene fluoride is (0.1-1.6) to 1 (14-20);
in the stirring process, the stirring temperature is 30-80 ℃, and the stirring time is 8-18 h.
7. The method for preparing polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning property as claimed in claim 1, wherein the non-solvent induced phase separation method comprises: and (3) coating the casting solution on a substrate in a blade mode, and placing the substrate in a gel bath for phase separation to obtain the polyvinylidene fluoride mixed matrix membrane.
8. The method for preparing polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance as claimed in claim 7, wherein the thickness of the scraped membrane is 100-260 μm;
the gel bath comprises a mixed solution of ethanol and water in a volume ratio of (0.5-1.5) to (0.8-1.3), and the temperature of the gel bath is 14-30 ℃.
9. Polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning properties, characterized in that it is prepared by the process according to any one of claims 1 to 8.
10. Use of the polyvinylidene fluoride mixed matrix membrane of claim 9 for combating organic contaminants.
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