CN113750826B - Preparation method of photocatalytic composite porous membrane - Google Patents
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- CN113750826B CN113750826B CN202010493037.8A CN202010493037A CN113750826B CN 113750826 B CN113750826 B CN 113750826B CN 202010493037 A CN202010493037 A CN 202010493037A CN 113750826 B CN113750826 B CN 113750826B
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- 239000012528 membrane Substances 0.000 title claims abstract description 163
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000007598 dipping method Methods 0.000 claims abstract description 48
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 44
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 28
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 21
- -1 sulfur ion Chemical class 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 22
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 11
- 230000015271 coagulation Effects 0.000 claims description 11
- 239000011941 photocatalyst Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 2
- 229910001447 ferric ion Inorganic materials 0.000 claims 2
- 238000007654 immersion Methods 0.000 claims 2
- 238000011068 loading method Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 27
- 230000015556 catabolic process Effects 0.000 abstract description 26
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- 230000004907 flux Effects 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000001112 coagulating effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000012467 final product Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 238000009295 crossflow filtration Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- CKKNXLXIMISLER-UHFFFAOYSA-N [Cu]=S.[S-2].[Cd+2] Chemical compound [Cu]=S.[S-2].[Cd+2] CKKNXLXIMISLER-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002120 nanofilm Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a preparation method of a photocatalytic composite porous membrane, which comprises the following steps: 1) Adding polyether sulfone and a pore-forming agent into an organic solvent, mixing, heating to 40-80 ℃, continuously stirring for 2-7h to obtain a membrane casting solution, carrying out blade coating, curing in coagulating bath water to form a membrane, and drying at room temperature to obtain a polyether sulfone porous membrane; 2) Sequentially dipping the obtained polyether sulfone porous membrane in a cadmium ion solution, deionized water, a sulfur ion solution and deionized water to finish a dipping cycle, namely cycle A, repeating cycle A for a plurality of times, and synthesizing cadmium sulfide on the surface of the polyether sulfone porous membrane to obtain the polyether sulfone/cadmium sulfide porous membrane; 3) And (3) dipping the polyether sulfone/cadmium sulfide porous membrane in an iron ion solution, and then dipping in pyrrole to synthesize polypyrrole to obtain the photocatalytic composite porous membrane. The photocatalytic composite porous membrane can realize dynamic degradation of pollutants in water under high water flux, overcomes the problem of membrane pollution generated during continuous dead-end filtration, and has low operation cost and wide application prospect.
Description
Technical Field
The invention belongs to the field of membrane materials, and particularly relates to preparation of a photocatalytic composite porous membrane with a separation function and photocatalytic degradation of organic matters.
Background
With the increasing discharge amount of waste water, the problem of organic waste water pollution becomes more and more serious, which brings great challenges to the living environment of human beings, and the waste water treatment is paid more and more attention. The organic waste water treatment method comprises a separation method and a conversion method, and a membrane separation technology for treating waste water by using a membrane material is one of the separation methods. The traditional membrane separation technology utilizes the selective permeability of a membrane to separate pollutants in water, and adjusts the pore diameter and the surface performance of the membrane material to improve the separation performance. The polyether sulfone membrane material has good chemical stability and temperature stability, simple preparation process and mature commercialization technology, and is widely applied to the field of wastewater treatment. The single polyether sulfone porous membrane has serious pollution problem, in order to solve the problem, celik and the like design a carbon nanotube blended polyether sulfone porous membrane to be applied to sewage treatment, the membrane pollution problem of the polyether sulfone porous membrane is effectively relieved by adding carbon nanotubes, but the cost of the carbon nanotubes is high, so that the cost is obviously increased, and the technology is disclosed in Water research 2011 volume 45, no. 1, pages 274-282, article subjects: scale control in water treatment of Carbon nanotube polyethersulfone blended membranes, i.e. Carbon nanotube grafted polymeric sulfonic membranes for filtration control in water treatment, water Research,2011, 45 (1): 274-282.. Generally, the smaller the pore size of the membrane material is, the smaller the particle size of the contaminant can be separated, the higher the rejection rate is, but at the same time, the larger the resistance of the water flow is, the lower the membrane flux is, and the more serious the membrane contamination problem is. Therefore, the polyethersulfone membrane material often needs to be modified or compounded with other materials to alleviate the membrane pollution problem. The patent number 201710842388.3 discloses a preparation method of a modified activated carbon fiber composite polyether sulfone ultrafiltration membrane, and an obtained ultrafiltration membrane and application thereof.
The photocatalysis technology is a cleaning technology, can decompose organic pollutants into carbon dioxide, water and small molecular inorganic substances under sunlight, and shows good organic wastewater treatment capacity. Cadmium sulfide is a narrow band gap semiconductor material, has the forbidden band width of 2.4eV, has good visible light responsibility and high catalytic efficiency, is simple in preparation process, and can be used for degrading organic pollutants. The preparation method of the magnesium-doped cadmium sulfide polyvinyl alcohol composite nano film by Krishhnakumar and the like realizes the efficient degradation of methylene blue solution under visible light, and the technology is disclosed in the journal of Material science: electronic materials, volume 28, 18, th period 13990-13999 in 2017, title of the article: the transparent magnesium-doped cadmium sulfide-polyvinyl alcohol nano composite membrane enhances the photocatalytic degradation of methylene blue under visible light, namely, enhancement of photocatalytic degradation of methyl blue under visible light, namely, enhanced Mg-doped CdS-PVA nanocomposite films, journal of Materials Science: materials in Electronics,2017, 28 (18): 13990-13999.. However, the single cadmium sulfide photocatalyst has poor stability, is easy to generate light corrosion in the photocatalysis process, and can obviously improve the stability of the cadmium sulfide by compounding with polypyrrole. Hiragond et al compared the effect of polythiophene, polypyrrole and polyaniline on the photocatalytic efficiency of cadmium sulfide quantum dots, found that the enhancement effect of polypyrrole on the photocatalytic efficiency of cadmium sulfide is most obvious, and disclosed in vacuum 2018, volume 155, 155: pages 159-168, article title: research on real-time photocatalytic activity of cadmium sulfide quantum dot sensitized conductive polymers, namely polythiophene, polypyrrole and polyaniline, namely combining the real-time photocatalytic activity of CdS QDs sensitive polymers: fed PTh, PPy and pani. Vacuum,2018, 155:159-168.. At present, most of cadmium sulfide photocatalysis is in nanometer level, and the macroscopic form is powder. In the using process, the powdery cadmium sulfide is mixed with the organic wastewater to effectively degrade organic pollutants, but the recovery of the cadmium sulfide photocatalyst is very difficult. Zhang Jie et al disclose a preparation method of cadmium sulfide-copper sulfide nano composite photocatalyst, which alleviates the photo-corrosion phenomenon of cadmium sulfide, but the recovery of the photocatalyst is still very difficult, see 'a preparation method of CdS-CuS nano composite photocatalyst', patent number 201710406905.2. A large amount of manpower and material resources are consumed in the catalyst recovery process, and the secondary pollution of the water body can be caused due to incomplete recovery. Therefore, the combination of the photocatalysis technology and the membrane material can not only promote the membrane separation and the pollutant degradation process, but also solve the problem of difficult recovery of the photocatalyst.
The existing photocatalytic porous membrane generally has higher interception and filtration performance, and the cross-flow filtration method is usually adopted to realize the functions of degrading and intercepting organic pollutants simultaneously. Li et al prepared a PDA/ZIF-67 modified polypropylene porous Membrane with Self-cleaning function for wastewater treatment, degrading pollutants under visible light to slow down Membrane pollution, but the photocatalytic degradation of pollutants was very limited due to the rapid flow of water over the Membrane surface in the cross-flow filtration mode, which was disclosed in "journal of Membrane science" 2019, volume 117341, self-cleaning PDA/ZIF-67@ PP Membrane for water wave communication with peroxide synthesis and visible light activity. Journal of Membrane science,2019, 591:117341.. The photocatalytic porous membrane with higher interception and filtration performance can work for a longer time in a cross-flow filtration mode, but the defect that cross-flow filtration is difficult to overcome is the low water flux, and after long-time operation, pollutants can be accumulated on the surface of the membrane to block membrane pores, so that membrane pollution is caused. The flux of the polluted photocatalytic porous membrane is sharply reduced, and the wastewater purification efficiency is greatly reduced. The preparation method of the photocatalytic composite porous membrane provided by the invention aims to be applied to a dead-end filtration process by regulating and controlling the raw material ratio and the membrane preparation process of the porous membrane, realizes photocatalytic degradation of pollutants in water under high water flux while keeping large water yield, and overcomes the problem of membrane pollution.
In conclusion, in the wastewater treatment process, the existing polyether sulfone membrane separation technology has the problems of serious membrane pollution and incapability of degrading pollutants, and the photocatalytic technology has the problem of difficult recovery of a powdery photocatalyst. The photocatalytic separation membrane combining the photocatalytic technology and the membrane separation technology is only suitable for the cross-flow filtration process, so that the effect of relieving membrane pollution by photocatalysis is very limited. Therefore, the preparation of the photocatalytic film material which is easy to recover, can efficiently degrade pollutants and is pollution-resistant is very important.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a photocatalytic composite porous membrane, which is characterized in that a polyether sulfone porous membrane is loaded with cadmium sulfide and polypyrrole to obtain the photocatalytic composite porous membrane which is easy to recover, resistant to pollution, long in service time and high in catalytic efficiency.
Therefore, the technical scheme of the invention is as follows:
a preparation method of a photocatalytic composite porous membrane comprises the following steps:
1) Preparing a polyether sulfone porous base membrane: adding polyether sulfone and a pore-forming agent into an organic solvent for mixing, heating in a water bath to 40-80 ℃, continuously stirring for 2-7 hours to obtain a membrane casting solution, blade-coating, curing in a deionized water coagulation bath to form a membrane, and drying at room temperature to obtain a porous membrane I;
2) Dipping the porous membrane I obtained in the step 1) in a cadmium ion solution, deionized water, a sulfur ion solution and deionized water in sequence to finish a dipping cycle called cycle A, repeating the cycle A for a plurality of times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in an iron ion solution, and then dipping in a pyrrole solution to synthesize polypyrrole to obtain the photocatalytic composite porous membrane.
Further optimizing the technical scheme, in the step 1), the pore-forming agent is selected from any one of polyvinylpyrrolidone and polyethylene glycol, and the organic solvent is selected from any one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
The technical scheme is further optimized, in the step 1), the content of the polyether sulfone is 11-15 wt.%, the content of the pore-forming agent is 5-13 wt.%, and the balance is the organic solvent.
Further optimizing the technical scheme, the cadmium ion solution in the step 2) is any one of a cadmium chloride solution and a cadmium nitrate solution, and the sulfur ion solution is any one of an ammonium sulfide solution and a sodium sulfide solution. The concentration of the cadmium ion solution in the step 2) is 0.1-2M, and the concentration of the sulfur ion solution is 0.1-2M. The concentration ratio of the cadmium ion solution to the sulfur particle solution in the step 2) is 1: 1.
Further optimizing the technical scheme, the repetition frequency of the circulation A in the step 2) is 5-25 times.
Further optimizing the technical scheme, the iron ion solution in the step 3) is any one of ferric chloride solution and ferric nitrate solution, the concentration of the iron ion solution is 0.1-2M, and the concentration of the pyrrole solution is 0.1-2M.
Further optimizing the technical scheme, the dipping time of the porous membrane II in the ferric nitrate solution in the step 3) is 1-10 min, and the dipping time of the porous membrane II in the pyrrole solution is 1-10 min.
The invention firstly prepares the polyether sulfone porous membrane, and the cadmium sulfide and the polypyrrole are deposited on the surface of the polyether sulfone porous membrane in sequence. The polypyrrole can increase the binding force of the photocatalyst and the polyether sulfone porous membrane, and can be used as a conductive substance to separate photoproduction electrons from holes in time, so that the quantum efficiency is improved, and the photo-corrosion phenomenon of cadmium sulfide is inhibited. The device is shown in figure 1, methylene blue solution is used for simulating organic wastewater, a peristaltic pump is used as a negative pressure source of water flow, the diameter of a sample of the photocatalytic composite porous membrane is 4.5cm, the water flow is 30mL/h, a light source is provided by a 500W xenon lamp, and the visible light intensity of the surface of the sample is 100mW/cm 2 And running the sample for 24 hours, respectively testing the absorbance values of the methylene blue solution before and after each 1 hour of treatment, and calculating the dynamic degradation rate of the photocatalytic composite porous membrane. Under the test condition, the average dynamic degradation rate of the prepared photocatalytic composite porous membrane in 24h reaches 40-52%, the dynamic degradation rate in 24h reaches 40-50%, the dynamic degradation of methylene blue solution under high water flux is realized, the problem of membrane pollution is hardly caused by continuous operation, the preparation process is simple, the cost is low, the recovery is easy, and the method can be applied to the purification of organic wastewater such as dye wastewater.
Drawings
FIG. 1 is a schematic diagram of a photocatalytic reactor in test I.
Fig. 2 shows the dynamic degradation of the photocatalytic composite porous membrane prepared in example 1 to a methylene blue solution.
Detailed Description
The technical solution of the present invention is described in detail below with reference to examples.
Example 1
A preparation method of a photocatalytic composite porous membrane comprises the following steps:
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a film, and drying at room temperature to obtain a porous film I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to finish a dipping cycle, namely cycle A, repeating the cycle A for 10 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in 0.1M ferric nitrate solution for 2min, and then dipping in 0.1M pyrrole solution for 2min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
The final product prepared in this example was tested for catalytic efficiency, and the average dynamic degradation rate in 24h was as shown in fig. 2, the average dynamic degradation rate in 24h reached 52%, and the dynamic degradation rate in 24h reached 50%.
Example 2
1) Preparing a polyether sulfone porous base membrane: mixing 15wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 75wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a membrane, and drying at room temperature to obtain a porous membrane I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to complete a dipping cycle, namely cycle A, repeating the cycle A for 10 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in a 0.1M ferric nitrate solution for 2min, and then dipping in a 0.1M pyrrole solution for 2min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
The final product prepared in the embodiment is subjected to a catalytic efficiency test, and the result shows that the average dynamic degradation rate in 24 hours reaches 52%, and the dynamic degradation rate in 24 hours reaches 50%.
Example 3
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a film, and drying at room temperature to obtain a porous film I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium nitrate solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to complete a dipping cycle called cycle A, repeating the cycle A for 10 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in a 0.1M ferric nitrate solution for 2min, and then dipping in a 0.1M pyrrole solution for 2min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
The final product prepared in the embodiment is subjected to a catalytic efficiency test, and the result shows that the average dynamic degradation rate in 24 hours reaches 52%, and the dynamic degradation rate in 24 hours reaches 50%.
Example 4
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a film, and drying at room temperature to obtain a porous film I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M sodium sulfide solution and deionized water in sequence to finish a dipping cycle, namely cycle A, repeating the cycle A for 10 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in a 0.1M ferric nitrate solution for 2min, and then dipping in a 0.1M pyrrole solution for 2min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
The final product prepared in the embodiment is subjected to a catalytic efficiency test, and the result shows that the average dynamic degradation rate in 24 hours reaches 52%, and the dynamic degradation rate in 24 hours reaches 50%.
Example 5
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a film, and drying at room temperature to obtain a porous film I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to finish a dipping cycle, namely cycle A, repeating the cycle A for 10 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in 0.1M ferric chloride solution for 2min, and then dipping in 0.1M pyrrole solution for 2min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
The final product prepared in the embodiment is subjected to a catalytic efficiency test, and the result shows that the average dynamic degradation rate in 24 hours reaches 52%, and the dynamic degradation rate in 24 hours reaches 50%.
Example 6
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a film, and drying at room temperature to obtain a porous film I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to finish a dipping cycle, namely cycle A, repeating the cycle A for 6 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in 0.1M ferric nitrate solution for 2min, and then dipping in 0.1M pyrrole solution for 2min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
In the embodiment, the final product is obtained, and the catalytic efficiency test is performed on the final product, and the result shows that the average dynamic degradation rate in 24 hours reaches 45%, and the dynamic degradation rate in 24 hours reaches 45%.
Example 7
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a membrane, and drying at room temperature to obtain a porous membrane I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to finish a dipping cycle, namely cycle A, repeating the cycle A for 14 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Soaking the porous membrane II obtained in the step 2) in 0.1M ferric nitrate solution for 2min, then soaking in 0.1M pyrrole solution for 2min, drying at room temperature, and depositing polypyrrole on the two surfaces of the porous membrane to obtain the photocatalytic composite porous membrane.
The final product prepared in the embodiment is subjected to a catalytic efficiency test, and the result shows that the average dynamic degradation rate in 24 hours reaches 47%, and the dynamic degradation rate in 24 hours reaches 47%.
Example 8
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a film, and drying at room temperature to obtain a porous film I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to finish a dipping cycle, namely cycle A, repeating the cycle A for 10 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in 0.1M ferric nitrate solution for 2min, and then dipping in 0.1M pyrrole solution for 1min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
The final product prepared in the embodiment is subjected to a catalytic efficiency test, and the result shows that the average dynamic degradation rate in 24 hours reaches 50%, and the dynamic degradation rate in 24 hours reaches 45%.
Example 9
1) Preparing a polyether sulfone porous base membrane: mixing 13wt.% of polyether sulfone, 10wt.% of polyvinylpyrrolidone and 77wt.% of dimethylacetamide, heating in a water bath to 75 ℃, continuously stirring for 6 hours, blade-coating, curing in a deionized water coagulation bath to form a membrane, and drying at room temperature to obtain a porous membrane I;
2) Dipping the porous membrane I obtained in the step 1) in 0.1M cadmium chloride solution, deionized water, 0.1M ammonium sulfide solution and deionized water in sequence to finish a dipping cycle, namely cycle A, repeating the cycle A for 10 times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in 0.1M ferric nitrate solution for 2min, and then dipping in 0.1M pyrrole solution for 6min to synthesize polypyrrole, so as to obtain the photocatalytic composite porous membrane.
The final product prepared in the embodiment is subjected to a catalytic efficiency test, and the result shows that the average dynamic degradation rate in 24 hours reaches 50%, and the dynamic degradation rate in 24 hours reaches 48%.
Claims (7)
1. A preparation method of a photocatalytic composite porous membrane is characterized by comprising the following steps: preparing a polyether sulfone porous base membrane, loading a photocatalyst on the surface of the polyether sulfone porous base membrane, and then depositing polypyrrole on the surface of the photocatalyst to form the photocatalyst composite porous membrane, wherein the preparation method comprises the following steps:
1) Preparing a polyether sulfone porous base membrane: adding polyether sulfone and a pore-forming agent into an organic solvent for mixing, heating to 40-80 ℃ in a water bath, continuously stirring for 2-7h to obtain a membrane casting solution, carrying out blade coating, curing in a deionized water coagulation bath to form a membrane, and drying at room temperature to obtain a porous membrane I;
2) Dipping the porous membrane I obtained in the step 1) in a cadmium ion solution, deionized water, a sulfur ion solution and deionized water in sequence to finish a dipping cycle called cycle A, repeating the cycle A for a plurality of times, and synthesizing cadmium sulfide on the surface of the porous membrane I to obtain a porous membrane II;
3) Dipping the porous membrane II obtained in the step 2) in an iron ion solution, and then dipping in an pyrrole solution to synthesize polypyrrole to obtain the photocatalytic composite porous membrane.
2. The method for preparing the photocatalytic composite porous membrane as claimed in claim 1, wherein the pore-forming agent in step 1) is selected from any one of polyvinylpyrrolidone and polyethylene glycol, and the organic solvent is selected from any one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
3. The preparation method of the photocatalytic composite porous membrane according to claim 1, wherein the polyether sulfone content in the step 1) is 11 to 15wt.%, and the pore-forming agent content is 5 to 13wt.%.
4. The preparation method of the photocatalytic composite porous membrane according to claim 1, wherein the cadmium ion solution in step 2) is any one of a cadmium chloride solution and a cadmium nitrate solution, and the sulfur ion solution is any one of an ammonium sulfide solution and a sodium sulfide solution; the concentration of the cadmium ion solution in the step 2) is 0.1-2M, and the concentration of the sulfur ion solution is 0.1-2M; the concentration ratio of the cadmium ion solution to the sulfur ion solution in the step 2) is 1: 1.
5. The method of claim 1, wherein the cycle A in step 2) is repeated 5 to 25 times.
6. The method for preparing a photocatalytic composite porous membrane according to claim 1, wherein the ferric ion solution in step 3) is any one of a ferric chloride solution and a ferric nitrate solution, the concentration of the ferric ion solution is 0.1 to 2M, and the concentration of the pyrrole solution is 0.1 to 2M.
7. The preparation method of the photocatalytic composite porous membrane as claimed in claim 1, wherein the immersion time of the porous membrane II in the iron ion solution in step 3) is 1 to 10min, and the immersion time of the porous membrane II in the pyrrole solution is 1 to 10min.
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