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Based on non-metal multi-doped ntio 2 Visible light-catalyzed flat-plate ultrafiltration membrane and preparation method thereof

A multi-doped, non-metallic technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of inability to prepare separation membranes and complicated separation membrane preparation processes , did not pass and other problems, to achieve good photocatalytic degradation performance and anti-pollution performance, anti-pollution and visible light catalytic activity improvement, resistance increase coefficient and contact angle reduction effect

Active Publication Date: 2019-12-03
UNIV OF JINAN
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Chinese patent CN102989329A passed AgNO 3 、TiO 2 Blending modification to prepare ultrafiltration membranes, in fact, mainly uses AgNO 3 visible light catalytic activity, and the degradation rate is slow (in the patent, the degradation rate of methylene blue is characterized by light for 10 hours), and it is impossible to prepare a separation membrane for separation and visible light catalysis at the same time; 3 PO 4 / TiO 2 Complex (Ag 3 PO 4 Nanoparticle deposition onto TiO 2 Surface) and polyvinylidene fluoride materials are blended and modified, so that the modified film has visible light catalytic antibacterial and antifouling properties, mainly using the deposited on TiO 2 Ag on the surface 3 PO 4 Particles degrade the organic matter adsorbed during the application of the separation membrane to reduce membrane fouling, and have not been used to prepare a separation membrane with both separation and visible light catalytic properties; at the same time, neither of these two patents has made full use of silver salts and TiO through synergistic effects 2 The catalytic performance of silver salt or silver salt and TiO is only utilized by blending or deposition 2 Respective catalytic activity, visible light catalytic efficiency is low
Chinese patent CN102895888A prepares a titanium dioxide / polyvinylidene fluoride film first, then absorbs and reduces silver ions on its surface to prepare a visible light-responsive polyvinylidene fluoride film, and the methylene blue degradation rate of the prepared film is 33% to 51% (visible light irradiation 100mins); however, this invention needs to complete the preparation of the patented product after the preparation of the titanium dioxide / polyvinylidene fluoride film, and then through the steps of absorbing silver ions, reducing silver ions to simple silver, and vacuum drying, and the preparation process requires a darkroom, Ultraviolet irradiation, vacuum drying and other conditions, the process is complicated, the preparation cost is high, and the industrialization is difficult
Chinese patent CN104383821A uses graphene oxide to support magnetic particles with a core-shell structure @TiO 2 The modified separation membrane was prepared, and it was believed that the separation membrane showed good photocatalytic degradation performance and protein pollution resistance performance for the target pollutant bovine serum albumin, but the separation performance and visible light catalytic degradation performance of the prepared membrane were not clarified in the patent application advantages and disadvantages, and the preparation process of the separation membrane is complicated; at the same time, the magnetic particles @TiO 2 The preparation method is complicated and the cost is high
The present invention adopts nTiO 2 Multi-doping of non-metals to give full play to a variety of non-metals and nTiO 2 The synergistic effect further enhances the nTiO 2 Visible light catalytic activity, and using non-metal multi-doped nTiO 2 Improving the visible light photocatalytic properties of polymer ultrafiltration membranes and preparing planar mixed matrix ultrafiltration membranes with visible light catalytic activity can significantly improve the photocatalytic properties of polymer ultrafiltration membranes. There have been no relevant literature reports at home and abroad.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] 71.0% (w / w) of dimethylacetamide, 13.0% (w / w) of polyethylene glycol 400, 0.5% (w / w) of Tween-80 and 2.5% (w / w) of sulfur nitrogen doped nTiO 2 Add them into three-neck round-bottomed flasks according to a certain order, and stir evenly; then add 13.0% (w / w) polysulfone, and stir and dissolve at 70°C for 7 hours until completely dissolved; then, the obtained casting solution Stand still for 16 hours at the temperature of stirring and dissolving to remove the remaining air bubbles in the casting solution.

[0027] Pour the defoamed casting solution on a clean glass plate, use a special flat film scraper to scrape it into a film, stay in the air for 15 seconds, and then immerse it in a constant temperature coagulation bath at 25°C to solidify and form. After the film is formed, it will automatically Take the film out of the glass plate, wash it with deionized water for 24 hours, and soak it in 50% glycerol for 48 hours to prepare nTiO based on sulfur and nitrogen doping....

Embodiment 2

[0030] Doping nTiO with sulfur and nitrogen 2 Content is reduced to 0.05% (w / w) by 2.5% (w / w), and the content of dimethylacetamide is increased to 73.45% (w / w) by 71.0% (w / w), all the other are the same as embodiment 1 . Then the prepared nTiO based on sulfur and nitrogen doping 2 The pure water flux of the visible light-catalyzed flat-plate ultrafiltration membrane is 403.95 L / m 2 ·hr·0.1MPa, the retention rate of bovine serum albumin was 92.14%, the coefficient of resistance increase was 1.73, and the contact angle was 84.4°; the degradation and removal rate of fulvic acid increased from 28.63% (without light, running for 1 hour) to 39.72 % (under simulated visible light, run for 1 hour).

Embodiment 3

[0032] Doping nTiO with sulfur and nitrogen 2 Content is brought up to 5.0% (w / w) by 2.5% (w / w), and the content of dimethylacetamide is reduced to 68.5% (w / w) by 71.0% (w / w), and all the other are with embodiment 1 . Then the prepared nTiO based on sulfur and nitrogen doping 2 The pure water flux of the visible light-catalyzed flat-plate ultrafiltration membrane is 507.51 L / m 2 ·hr·0.1MPa, the bovine serum albumin retention rate is 91.13%, the resistance increase coefficient is 1.28, and the contact angle is 71.5°; the degradation and removal rate of fulvic acid is increased from 41.57% (no light, run for 1 hour) to 68.46 % (under simulated visible light, run for 1 hour).

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Abstract

The invention discloses a non-metal multi-doped nTiO 2 The visible light catalytic flat ultrafiltration membrane and its preparation method belong to the field of membrane separation technology. Mix 8.0% to 20.0% (w / w) polysulfone or polyethersulfone, 5.0% to 15.0% (w / w) porogen, 0.05% to 2.0% (w / w) surfactant, 0.05% to 5.0 %(w / w)Non-metal multi-doped nTiO 2 Add 58.0% to 86.9% (w / w) solvent into a three-necked round-bottomed flask in a certain order, stir and dissolve at 30 to 80°C for 5 to 16 hours until completely dissolved, and leave to defoam for 8 to 24 hours. Make a film casting liquid; use the phase inversion method to scrape the film on a clean glass plate to prepare a visible light catalytic flat ultrafiltration membrane. The pure water flux of the ultrafiltration membrane prepared by the invention is ≥450L / m 2 ·hr·0.1MPa, the bovine serum albumin rejection rate is ≥90.00%, the degradation and removal rate of fulvic acid reaches about 65% (under simulated visible light, running for 1 hour), and has good anti-pollution performance and visible light catalytic performance. The product of the invention is particularly suitable for treatment of micro-polluted water sources, seawater desalination pretreatment, treatment and reuse of wastewater in the fields of biology, chemical industry, and medicine.

Description

technical field [0001] The invention relates to a polymer mixed matrix ultrafiltration membrane and a preparation method thereof, in particular to a non-metal multi-doped nTiO 2 Visible light catalytic flat-plate ultrafiltration membrane and preparation method thereof. Background technique [0002] The scarcity of water resources and increasingly serious water pollution have become bottlenecks restricting social progress and economic development. The development of new water sources and the utilization of waste water resources have also become issues of global concern. Due to the extremely rich water resources in Shanghai and the large amount of waste water generated, the recycling of sewage and seawater desalination have become strategic choices to solve the water resource crisis. Among many sewage resource technologies, membrane separation technology is one of the best choices. [0003] Mixed matrix membrane, also known as hybrid membrane, is a membrane formed by chemica...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01D69/06B01D69/02B01D61/14B01D67/00B01D71/68B01D71/02B01J31/38
CPCB01D61/145B01D67/0079B01D69/02B01D69/06B01D71/024B01D71/68B01J31/38B01J35/39
Inventor 王秀菊王立国许伟颖刘思全侯凯周凯丽王仲鹏何芳
Owner UNIV OF JINAN