CN114602552A - Photocatalytic composite membrane and preparation method and application thereof - Google Patents
Photocatalytic composite membrane and preparation method and application thereof Download PDFInfo
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- CN114602552A CN114602552A CN202210406269.4A CN202210406269A CN114602552A CN 114602552 A CN114602552 A CN 114602552A CN 202210406269 A CN202210406269 A CN 202210406269A CN 114602552 A CN114602552 A CN 114602552A
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- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 claims abstract description 51
- 239000010410 layer Substances 0.000 claims abstract description 18
- 239000000648 calcium alginate Substances 0.000 claims abstract description 15
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 15
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 15
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical group [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 239000002346 layers by function Substances 0.000 claims abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000004952 Polyamide Substances 0.000 claims description 37
- 229920002647 polyamide Polymers 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000004695 Polyether sulfone Substances 0.000 claims description 10
- 229920006393 polyether sulfone Polymers 0.000 claims description 10
- 239000000661 sodium alginate Substances 0.000 claims description 10
- 235000010413 sodium alginate Nutrition 0.000 claims description 10
- 229940005550 sodium alginate Drugs 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000013310 covalent-organic framework Substances 0.000 claims description 2
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 231100000049 endocrine disruptor Toxicity 0.000 claims description 2
- 239000000598 endocrine disruptor Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
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- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229960005309 estradiol Drugs 0.000 description 10
- 229930182833 estradiol Natural products 0.000 description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
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- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a photocatalytic composite membrane, which comprises a substrate filter membrane and a photocatalytic functional layer, wherein the substrate filter membrane is a microporous filter membrane with the aperture of 0.1-5 microns, the photocatalytic functional layer is a calcium alginate gel layer containing a photocatalyst, the thickness of the photocatalytic functional layer is 5-500 nanometers, and the particle size of the photocatalyst in the photocatalytic layer is 10-400 nanometers. The invention also relates to a preparation method and application of the photocatalytic composite membrane. The transparent calcium alginate gel layer on the surface of the filter membrane of the photocatalytic composite membrane is beneficial to the absorption of a photocatalyst to light, so that the photocatalytic composite membrane has good photocatalytic activity and stability, and can realize the efficient removal of organic pollutants and heavy metal ions in wastewater.
Description
Technical Field
The invention belongs to the field of materials, and relates to a visible light catalytic composite membrane, a preparation method thereof and application thereof in removing organic pollutants and heavy metal ions in wastewater under the condition of visible light.
Background
As the early economic development does not pay attention to ecological protection and ecological restoration, the water ecology and the ecological environment are greatly polluted and destroyed, and most of surface and underground water resources in China are polluted to different degrees. Various medical wastewater and dye wastewater contain a large amount of organic pollutants, and various heavy metal wastewater contains a large amount of inorganic heavy metal ions, so that the wastewater has great harm to organisms, and how to effectively remove various organic pollutants and heavy metal ions is an important problem in the water treatment process.
The membrane technology can efficiently remove various trace harmful pollutants through various mechanisms such as physical blocking, adsorption, retention and separation, has the advantages of greenness, high efficiency and no pollution, and has great potential in various industrial processes related to separation. However, in long-term use, due to the adsorption of contaminants on the membrane surface or in the pores of the membrane, the accumulation of fouling results in irreversible fouling, which leads to a drastic flux drop and a short membrane life due to frequent washing. Also, the additional energy and chemicals required for membrane regeneration and the additional treatment process add to the overall operating cost, limiting its practical application to some extent. Therefore, various studies have been made to improve the antifouling property of the film.
Photocatalytic processes can effectively and economically eliminate pollutants and bacteria through chemical redox processes. Nowadays, attempts have been made to prepare photocatalytic films by surface coating and blending methods to solve the problems of film contamination and difficulty in recycling of powdered photocatalysts. The surface coating method is an ideal method for preparing the photocatalytic film, wherein the photocatalyst is loaded on the surface of the film, can be fully contacted with pollutants, and does not influence the structure of the original film compared with the blending method. However, for such films, ensuring the effectiveness of the active functional layer and the stable loading of the photocatalyst are important issues to be solved.
CN113000071A discloses a porous visible light photocatalysis ZnFe2O4-TiO2A preparation and regeneration method of a PVDF composite membrane. Wherein ZnFe with rich pores is obtained by a sol-gel method2O4-TiO2PVDF membrane material, dye wastewater pollutants can enter the membrane and contact photocatalysis in the membraneThe surface area of the photocatalytic composite film can be increased by the aid of the agent, and light can well irradiate into the holes. However, the mixing of the photocatalyst lowers the mechanical strength of the PVDF film, and the stability is lowered.
CN112756001A discloses a preparation method of a floatable photocatalytic film with a photo-thermal function, which is characterized in that nano silver sulfide grows on the surface of nano spherical bismuth sulfide as a base to prepare a photocatalyst in a core-shell shape; and then cleaning the surface of the carbon cloth, and loading the photocatalyst on the surface of the carbon cloth in an ultrasonic mode. However, the combination of the catalyst and the carbon cloth is unstable only by means of ultrasound, which may cause the loss of the powdered photocatalyst and secondary pollution.
Aiming at the problems in the prior art, the invention discloses a photocatalytic composite membrane, which is provided with a transparent gel layer formed by crosslinking sodium alginate and calcium chloride on a microfiltration membrane, so that a photocatalyst is stably loaded on the surface of the membrane, the photocatalytic activity of the photocatalyst is favorably maintained, the problems of membrane pollution and difficulty in recycling of the powder photocatalyst are effectively solved, and the organic pollutants and heavy metal ions in wastewater are efficiently removed.
Disclosure of Invention
The invention aims to provide a photocatalytic composite membrane, wherein a photocatalyst is embedded into a transparent calcium alginate gel layer, so that the stable loading of the composite membrane is realized, and the original photocatalytic activity is kept; and the sodium alginate gel layer has good light transmission, can improve the utilization rate of light and enhance the photocatalysis effect, thereby realizing the high-efficiency removal of organic pollutants and heavy metal ions in water.
The specific technical scheme of the invention is as follows:
a photocatalytic composite membrane comprises a base filter membrane and a photocatalytic functional layer, wherein the aperture of the base filter membrane is 0.001-5 microns; the photocatalytic functional layer is a calcium alginate gel layer containing a photocatalyst, the thickness of the photocatalytic functional layer is 5-500 nanometers, and the particle size of the photocatalyst in the photocatalytic layer is 10-400 nanometers.
The base filter membrane material is one or more of polyether sulfone (PES), Polysulfone (PS), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Polyamide (PA), Polyacrylonitrile (PAN), polyvinyl chloride (PVC), sulfonated polyether sulfone (SPES), Sulfonated Polysulfone (SPS) and Cellulose (CNF).
The photocatalyst material is one or more of single-component photocatalyst and heterojunction photocatalyst in titanium dioxide, carbon nitride, bismuth tungstate, bismuth oxybromide, zinc oxide, bismuth vanadate, molybdenum disulfide, cadmium sulfide, bismuth molybdate, tungsten oxide, metal organic framework compound and covalent organic framework compound.
The invention further relates to a preparation method of the photocatalytic composite membrane, which comprises the following steps:
(1) dispersing a certain amount of sodium alginate and a photocatalyst in deionized water, and stirring and ultrasonically treating to obtain a uniform dispersion liquid;
(2) carrying out vacuum filtration on the dispersion liquid obtained in the step (1) on a filter membrane, and pumping water to dryness;
(3) taking down the filter membrane in the step (2), and drying;
(4) and (4) soaking the filter membrane obtained in the step (3) in a calcium chloride solution for crosslinking, washing the crosslinked filter membrane with deionized water, and drying to obtain the photocatalytic composite membrane with the photocatalyst embedded in the calcium alginate gel layer.
In the step (1), the mass of the sodium alginate is 2.5-40mg, the mass of the photocatalyst is 2.5-40mg, and the volume of the deionized water is 5-20 mL; the stirring time is 20-60 minutes, and the rotating speed is 200-800 revolutions per minute for magnetic stirring; the ultrasonic power is 100-1000W, the ultrasonic frequency is 10-50kHz, and the ultrasonic time is 10-30 minutes.
In the step (2), the pressure value of the vacuum filtration is-0.1 bar.
In the step (3), the drying mode can be forced air drying or vacuum drying; the drying temperature is 50-80 ℃, and the drying time is 10-240 minutes.
In the step (4), the concentration of the calcium chloride solution is 0.1-5mol/L, and the volume of the calcium chloride solution is 5-20 mL; the drying mode can be air-blast drying or vacuum drying; the drying temperature is 50-80 ℃, and the drying time is 6-12 hours.
The invention further relates to the application of the photocatalytic composite membrane in removing organic pollutants and heavy metal ions in wastewater, for example, the photocatalytic composite membrane is used for removing endocrine disruptors such as estradiol, estrone and bisphenol A, dyes such as methyl orange, rhodamine B, methyl blue and the like, and heavy metal ions such as hexavalent chromium ions and hexavalent uranium ions.
Compared with the prior art, the invention has the following beneficial effects:
(1) the photocatalytic composite membrane is prepared by embedding the photocatalyst into the calcium alginate gel layer modified filter membrane, wherein the photocatalyst responding to visible light is embedded into the calcium alginate gel layer modified filter membrane, and the transparent calcium alginate gel layer stably loads the photocatalyst on the surface of the filter membrane, so that the utilization of the photocatalyst to light can be improved, and the original photocatalytic activity of the photocatalyst is kept. The method effectively solves the problems of membrane pollution and difficult recycling of the powder photocatalyst, and can effectively remove organic pollutants and heavy metal ions in the wastewater, for example, the photocatalytic efficiency of an estradiol aqueous solution with the concentration of 3mg/L reaches 99.5 percent in 240 minutes under visible light; for rhodamine B solution with the concentration of 10mg/L, the photocatalytic efficiency reaches 100 percent in 150 minutes under visible light.
(2) The photocatalytic composite membrane has the advantages of wide raw material source, low price, simple preparation method, strong operability, convenience for further large-scale industrial production and good application prospect in environmental purification and sewage treatment.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a photocatalytic composite membrane by embedding a photocatalyst into a filter membrane modified by a calcium alginate gel layer.
FIG. 2 is an SEM image of the photocatalytic composite membrane PA/5SA/15BPG prepared in example 2.
FIG. 3 shows FITR (a) and XRD (b) contrast graphs of the photocatalytic composite membrane PA/5SA/15BPG prepared in example 2 and the PA/5SA prepared in comparative example 1 and the PA/15BPG prepared in comparative example 2.
FIG. 4 is a graph comparing the removal performance of the photocatalytic composite membranes prepared in examples 1-3 (example 1(PES/5SA/15BPG), example 2(PA/5SA/15BPG) and example 3(CNF/5SA/15BPG) with that of PA/5SA prepared in comparative example 1 and PA/15BPG prepared in comparative example 2 against rhodamine B under visible light.
FIG. 5 is a graph comparing the removal performance of the photocatalytic composite films prepared in examples 1-3 (example 1(PES/5SA/15BPG), example 2(PA/5SA/15BPG) and example 3(CNF/5SA/15BPG) with the removal performance of estradiol under visible light for PA/5SA prepared in comparative example 1 and PA/15BPG prepared in comparative example 2.
FIG. 6 is a graph showing the results of dynamic removal and recycling experiments for degrading estradiol by the photocatalytic composite membrane PA/5SA/15BPG prepared in example 2: (a) a dynamic removal experiment; (b) and (5) recycling experiments.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are illustrative only and not limiting.
Example 1: preparation of PES/5SA/15BPG photocatalytic composite membrane
1) 5mg of sodium alginate and 15mg of Bi2WO6/pg-C3N4(BPG) the photocatalyst is dispersed in 5mL of deionized water, and after 500 revolutions per minute at normal temperature, magnetic stirring and ultrasonic treatment are carried out to obtain uniform dispersion liquid;
2) vacuum filtering the obtained uniform dispersion solution on a PES filter membrane with the diameter of 0.45 mu m and the diameter of 5cm under the pressure of-0.1 bar, and pumping water to be dry;
3) taking down the obtained filter membrane, and drying the filter membrane in a blast drying oven at 60 ℃ for 10 minutes;
4) and soaking the obtained filter membrane in 5mL of 0.5M calcium chloride solution for crosslinking, washing the crosslinked filter membrane with 20mL of deionized water for 3 times, and then placing the filter membrane in a forced air drying oven for drying at 60 ℃ for 2 hours to obtain the PES/5SA/15BPG photocatalytic composite membrane.
Example 2: preparation of PA/5SA/15BPG photocatalytic composite membrane
1) 5mg of sodium alginate and 15mg of Bi2WO6/pg-C3N4The photocatalyst is dispersed in 5mL deionized water, and is obtained after 500 revolutions per minute magnetic stirring and ultrasonic processing at normal temperatureA homogeneous dispersion;
2) vacuum filtering the obtained uniform dispersion solution on a PA filter membrane with the diameter of 5cm and the diameter of 0.45 mu m under-0.1 bar, and pumping water;
3) taking down the obtained filter membrane, and drying the filter membrane in a blast drying oven at 60 ℃ for 10 minutes;
4) and soaking the obtained filter membrane in 5mL of 0.5M calcium chloride solution for crosslinking, washing the crosslinked filter membrane with 20mL of deionized water for 3 times, and then placing the filter membrane in a forced air drying oven for drying at 60 ℃ for 2 hours to obtain the PA/5SA/15BPG photocatalytic composite membrane.
Example 3: preparation of CNF/5SA/15BPG photocatalytic composite membrane
1) 5mg of sodium alginate and 20mg of Bi2WO6/pg-C3N4The photocatalyst is magnetically stirred and ultrasonically treated in 5mL of deionized water at normal temperature at 500 rpm to obtain uniform dispersion liquid;
2) vacuum-filtering the obtained uniform dispersion solution on a CNF filter membrane with the diameter of 5cm and the diameter of 0.45 mu m under-0.1 bar, and drying the water;
3) taking down the obtained filter membrane, and drying the filter membrane in a blast drying oven at 60 ℃ for 10 minutes;
4) and soaking the obtained filter membrane in 5mL of 0.5M calcium chloride solution for crosslinking, washing the crosslinked filter membrane with 20mL of deionized water for 3 times, and then placing the filter membrane in a forced air drying oven for drying at 60 ℃ for 2 hours to obtain the CNF/5SA/15BPG photocatalytic composite membrane.
Comparative example 1: preparation of PA/5SA photocatalytic composite membrane
1) Dispersing 5mg of sodium alginate in 5ml of deionized water, magnetically stirring at normal temperature at 500 revolutions per minute, and performing ultrasonic treatment to obtain uniform dispersion liquid;
2) vacuum filtering the obtained uniform dispersion solution on a PA filter membrane with the diameter of 5cm and the diameter of 0.45 mu m under-0.1 bar, and pumping water;
3) taking down the obtained filter membrane, and drying the filter membrane in a blast drying oven at 60 ℃ for 10 minutes;
4) and soaking the obtained filter membrane in 5mL of 0.5M calcium chloride solution for crosslinking, washing the crosslinked filter membrane with 20mL of deionized water for 3 times, and then placing the filter membrane in an air-blast drying oven for drying at 60 ℃ for 2 hours to obtain the PA/5SA photocatalytic composite membrane.
Comparative example 2: preparation of PA/15BPG photocatalytic composite membrane
1) 15mg of Bi2WO6/pg-C3N4Dispersing the photocatalyst in 5mL of deionized water, magnetically stirring at normal temperature at 500 rpm, and performing ultrasonic treatment to obtain a uniform dispersion liquid;
2) vacuum filtering the obtained uniform dispersion solution on a PA filter membrane with the diameter of 5cm and the diameter of 0.45 mu m under-0.1 bar, and pumping water;
3) taking down the obtained filter membrane, and drying the filter membrane in a blast drying oven at 60 ℃ for 10 minutes;
4) and soaking the obtained filter membrane in 5mL of 0.5M calcium chloride solution for crosslinking, washing the crosslinked filter membrane with 20mL of deionized water for 3 times, and then placing the filter membrane in a forced air drying oven for drying at 60 ℃ for 2 hours to obtain the PA/515BPG photocatalytic composite membrane.
The products obtained in examples 1 to 3 and comparative examples 1 to 2 were tested:
respectively taking rhodamine B (RhB) and estradiol (E2) as target degradants, and investigating the photocatalytic performance of the photocatalytic composite membrane under visible light, wherein the visible light adopts a 500W xenon lamp as a light source and a 420nm filter, and the average light intensity is 30mW/cm2(ii) a Taking 30mL of 10mg/L rhodamine B solution or 3mg/L estradiol solution, placing the photocatalytic composite membrane in the solution, and stirring for 4 hours in a dark environment to ensure that the adsorption balance between the photocatalyst and the target pollutant is achieved; turning on a xenon lamp light source to start a photocatalytic reaction, taking 0.5mL of reaction solution every 10 minutes, and filtering supernate by using a 0.45-micron water system filter membrane; detecting the concentration of rhodamine B (551 nm) in the supernatant by an ultraviolet spectrophotometer; the concentration of estradiol (at 202 nm) in the supernatant was determined by High Performance Liquid Chromatography (HPLC) (Agilent-C18, acetonitrile/water volume ratio 62:38, flow rate 1 mL/min).
The test results are shown in table 1, and the results and analysis are as follows:
TABLE 1
FIG. 4 is a graph showing the degradation performance of the photocatalytic composite films prepared in examples 1-3 and comparative examples 1-2 on rhodamine B under visible light. As the photocatalyst is successfully loaded on the filter membrane, the PES/5SA/15BPG, PA/5SA/20BPG and CNF/10SA/15BPG of the examples 1-3 show good removal effect on rhodamine B, and the removal efficiency reaches 100 percent within 150 minutes of illumination; the removal rates of PA/SA and PA/15BPG of comparative examples 1-2 were 10.1% and 100%, respectively, but since the photocatalyst was only suction-filtered on the membrane surface in PA/15BPG, without being fixed by calcium alginate gel, a large amount of photocatalyst fell off during use, and could not be reused.
FIG. 5 is a graph comparing the degradation performance of the photocatalytic composite films prepared in examples 1-3 and comparative examples 1-2 to estradiol under visible light. The PES/5SA/15BPG, PA/5SA/20BPG, CNF/10SA/15BPG of examples 1-3 and PA/SA and PA/15BPG of comparative examples 1-2 respectively reach 47.0%, 78.5%, 47.0%, 73.7% and 72.8% after 180 minutes of adsorption, and respectively reach 93.2%, 99.5%, 91.0%, 74.5% and 91.1% after 240 minutes of photocatalysis, and the results show that the PA filter membrane has good adsorption and removal effects on estradiol, and the adsorption further promotes the photocatalysis process, so that the example 2 has the highest removal rate on estradiol; and because the PA/SA does not contain the photocatalyst, the removal rate is basically unchanged in the photocatalysis process, and because the PA/15BPG is not fixed by calcium alginate gel, a large amount of the photocatalyst falls off in the use process.
FIG. 6 is a graph showing the results of the static cycle (a) and dynamic cycle (b) experiments of the photocatalytic composite membrane PA/5SA/15BPG prepared in example 2. In the static cycle experiment, the removal efficiency of 1, 2, 3, 4 and 5 times of adsorption-photocatalysis cycles for 36 hours is 99.5%, 100%, 98.5%, 97.8% and 96.6% respectively; in dynamic cycle experiments, PA/5SA/15The adsorption of BPG to E2 reaches saturation, under the irradiation of visible light, the concentration of E2 decreases with the increase of the gravity filtration times, the removal rate of E2 finally reaches 95.1%, and the permeability of PA/5SA/15BPG is from 44.6L m because the BPG has good antifouling performance-2h-1bar-1Change to 45.2L m-2h-1bar-1And basically keeps stable. The result shows that the composite membrane has good photocatalytic activity and has high self-cleaning and removal rate to E2 under the condition of no adsorption. The PA/5SA/15BPG is shown to have good stability and durability in the process of removing E2.
It can be seen from the above examples and comparative examples that, in the photocatalytic composite membrane of the present invention, the photocatalyst is embedded in the filter membrane modified by the calcium alginate gel layer, and the transparent calcium alginate gel layer stably supports the photocatalyst on the surface of the filter membrane, thereby improving the utilization of the photocatalyst to light and maintaining the original photocatalytic activity. The method can effectively solve the problems of membrane pollution and difficult recycling of the powder photocatalyst, can realize efficient removal of pollutants, and has good stability and durability.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A photocatalytic composite membrane comprises a base filter membrane and a photocatalytic functional layer, wherein the aperture of the base filter membrane is 0.001-5 microns; the photocatalytic functional layer is a calcium alginate gel layer containing a photocatalyst, the thickness of the photocatalytic functional layer is 5-500 nanometers, and the particle size of the photocatalyst in the photocatalytic layer is 10-400 nanometers.
2. The photocatalytic composite membrane according to claim 1, wherein the base filter membrane material is selected from one or more of polyethersulfone, polysulfone, polyvinylidene fluoride, polytetrafluoroethylene, polyamide, polyacrylonitrile, polyvinyl chloride, sulfonated polyethersulfone, sulfonated polysulfone, and cellulose.
3. The photocatalytic composite film according to claim 1, wherein the photocatalyst is one or more of a single-component photocatalyst and a heterojunction photocatalyst containing titanium dioxide, carbon nitride, bismuth tungstate, bismuth oxybromide, zinc oxide, bismuth vanadate, molybdenum disulfide, cadmium sulfide, bismuth molybdate, tungsten oxide, a metal-organic framework compound, a covalent-organic framework compound.
4. A method of preparing a photocatalytic composite film according to any one of the preceding claims 1-3, comprising the steps of:
(1) dispersing a certain amount of sodium alginate and a photocatalyst in deionized water, and stirring and ultrasonically mixing to obtain a uniform dispersion liquid;
(2) carrying out vacuum filtration on the dispersion liquid obtained in the step (1) on a filter membrane, and pumping water to dryness;
(3) taking down the filter membrane in the step (2), and drying;
(4) and (4) soaking the filter membrane obtained in the step (3) in a calcium chloride solution for crosslinking, washing the crosslinked filter membrane with deionized water, and drying to obtain the photocatalytic composite membrane with the photocatalyst embedded in the calcium alginate gel layer.
5. The preparation method according to claim 4, wherein in the step (1), the mass of the sodium alginate is 2.5-40mg, the mass of the photocatalyst is 2.5-40mg, and the volume of the deionized water is 5-20 mL; the stirring time is 20-60 minutes, and the rotating speed is 200-800 revolutions per minute for magnetic stirring; the ultrasonic power is 100-1000W, the ultrasonic frequency is 10-50kHz, and the ultrasonic time is 10-30 minutes.
6. The method according to claim 4, wherein in step (2), the vacuum filtration has a pressure value of-0.1 bar.
7. The production method according to claim 4, wherein in step (3), the drying manner is air-blast drying or vacuum drying; the drying temperature is 50-80 ℃, and the drying time is 10-240 minutes.
8. The preparation method according to claim 4, wherein in the step (4), the concentration of the calcium chloride solution is 0.1-5mol/L, and the volume of the calcium chloride solution is 5-20 mL; the drying mode is blast drying or vacuum drying; the drying temperature is 50-80 ℃, and the drying time is 6-12 hours.
9. Use of the photocatalytic composite film according to any one of claims 1 to 3 for photocatalytic removal of organic pollutants and heavy metal ions in wastewater.
10. The use according to claim 9, wherein the organic contaminant is an endocrine disruptor, a dye.
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