CN115178110A - Sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics as well as preparation method and application thereof - Google Patents
Sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN115178110A CN115178110A CN202210823897.2A CN202210823897A CN115178110A CN 115178110 A CN115178110 A CN 115178110A CN 202210823897 A CN202210823897 A CN 202210823897A CN 115178110 A CN115178110 A CN 115178110A
- Authority
- CN
- China
- Prior art keywords
- membrane
- sewage treatment
- fenton
- photo
- organic framework
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 120
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 74
- 239000010865 sewage Substances 0.000 title claims abstract description 59
- 230000008929 regeneration Effects 0.000 title claims abstract description 38
- 238000011069 regeneration method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002033 PVDF binder Substances 0.000 claims abstract description 20
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000000614 phase inversion technique Methods 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000013177 MIL-101 Substances 0.000 claims description 24
- 239000000975 dye Substances 0.000 claims description 14
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 9
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003242 anti bacterial agent Substances 0.000 claims description 6
- 229940088710 antibiotic agent Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 230000004907 flux Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 19
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000003115 biocidal effect Effects 0.000 description 7
- 230000031700 light absorption Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 4
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 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 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229960003405 ciprofloxacin Drugs 0.000 description 2
- 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 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 229960004368 oxytetracycline hydrochloride Drugs 0.000 description 2
- 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 2
- 230000002195 synergetic effect Effects 0.000 description 2
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics, a preparation method and application thereof; the method comprises the following steps: preparing a metal organic framework material; dispersing a metal organic framework material and titanium dioxide in N, N-dimethylformamide, uniformly mixing, adding polyvinylidene fluoride and polyvinylpyrrolidone, and stirring in a water bath for a period of time to obtain a casting solution; after the membrane casting solution is subjected to ultrasonic defoaming treatment, a phase inversion method is adopted to prepare a membrane, and a sewage treatment membrane (CFT/PVDF) is obtained; the technical problems that the existing general powder adsorbent is difficult to recover and can cause secondary pollution, a filter membrane can effectively obstruct and separate organic pollutants, but the adsorption capacity and the membrane flux are reduced due to membrane pollution and the like in the prior art are solved through the proposal of the sewage treatment membrane material with the characteristics of efficient dynamic adsorption and photo-Fenton regeneration.
Description
Technical Field
The invention relates to the technical field of composite membrane materials, in particular to a sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics, and a preparation method and application thereof.
Background
The water crisis caused by the increasingly serious water pollution is a great challenge for mankind. When organic pollutants such as antibiotics and dyes widely exist in water environment, a series of ecological environment risks and health problems are caused. Therefore, how to remove the organic pollutants in the water body with high efficiency has become an urgent problem to be solved.
At present, various water pollution remediation methods such as adsorption, photocatalysis, biological treatment, chemical methods, etc. have been developed. Among them, the adsorption method is an attractive option due to its simple operation and low cost. However, the common powder adsorbent is difficult to separate and recover from the water body, and secondary pollution is caused. The filter membrane can effectively block and separate organic pollutants, but the problem that the membrane is polluted to cause the reduction of adsorption capacity and membrane flux is generally existed. Therefore, the filter membrane is effectively combined with the powder catalyst, so that high-efficiency dynamic adsorption is realized, and organic pollutants are catalytically decomposed in situ, thereby providing a more effective water treatment method.
Therefore, aiming at the problems, the invention provides a sewage treatment membrane material with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics, a preparation method and application thereof.
Disclosure of Invention
The invention aims to provide a sewage treatment membrane material with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics, a preparation method and application thereof, and the sewage treatment membrane material with the high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics is provided to solve the technical problems that the existing common powder adsorbent is difficult to recover, secondary pollution is caused, a filter membrane can effectively obstruct and separate organic pollutants, but the adsorption capacity and the membrane flux are reduced due to membrane pollution and the like in the prior art.
The invention provides a preparation method of a sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics, which is characterized by comprising the following steps: the method comprises the following steps:
preparing a metal organic framework material;
dispersing a metal organic framework material and titanium dioxide in N, N-dimethylformamide, uniformly mixing, adding polyvinylidene fluoride and polyvinylpyrrolidone, and stirring in a water bath for a period of time to obtain a casting solution;
and (3) after the membrane casting solution is subjected to ultrasonic defoaming treatment, preparing a membrane by adopting a phase inversion method to obtain the sewage treatment membrane (CFT/PVDF).
Preferably, the metal-organic framework material is metal-organic framework material MIL-101 (Co, fe) or metal-organic framework material MIL-101 (Fe).
Preferably, the metal organic framework material MIL-101 (Co, fe) is prepared by:
dissolving cobalt dichloride hexahydrate, ferric trichloride hexahydrate and 2-amino terephthalic acid in N, N-dimethylformamide, uniformly mixing, reacting at 110 ℃ for 20 hours, cooling to room temperature, collecting precipitate, and drying to obtain the powdery metal organic framework material MIL-101 (Co, fe).
Preferably, the mass ratio of the cobalt dichloride hexahydrate, the ferric trichloride hexahydrate, the 2-amino terephthalic acid and the N, N-dimethylformamide is 1.
Preferably, the mass ratio of the metal organic framework material powder to the titanium dioxide powder to the N, N-dimethylformamide to the polyvinylidene fluoride to the polyvinylpyrrolidone is (1-2): (3-4): 47, (1.5-2.5).
Preferably, the heating temperature of the water bath is 50-80 ℃, and the stirring is carried out for 3-6h under the water bath.
Preferably, the heating temperature of the water bath is 60 ℃, and the stirring is carried out for 5 hours under the water bath.
Preferably, the film preparation process by the phase inversion method comprises the following steps: taking a proper amount of membrane casting liquid on a glass plate, scraping to form a membrane, standing at room temperature for 2-5min, immersing in deionized water at room temperature to form a membrane, and then placing the membrane in new deionized water to be immersed for 10-20h for later use.
Preferably, the thickness of the sewage treatment membrane is 100-300 μm.
The invention also provides a sewage treatment membrane obtained based on the preparation method of the sewage treatment membrane with the efficient dynamic adsorption and photo-Fenton regeneration characteristics.
The invention also provides an application of the sewage treatment membrane in high-efficiency dynamic adsorption of various organic pollutants (dyes and antibiotics) in a water body.
Compared with the prior art, the invention provides a sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics, and the preparation method and the application thereof have the following progress:
1. the sewage treatment membrane provided by the invention is formed by uniformly distributing metal organic framework materials MIL-101 (Co, fe) and titanium dioxide on the surface and inside of a polyvinylidene fluoride membrane, and has the characteristics of high-efficiency organic pollutant adsorption and good light-Fenton regeneration.
2. The sewage treatment membrane provided by the invention has the regeneration efficiency close to 90% under the coexistence of light and hydrogen peroxide.
3. The sewage treatment membrane provided by the invention is prepared by adopting a phase inversion method, is simple to operate, has low cost and is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scanning electron microscope image of the surface of a sewage treatment membrane prepared according to a first embodiment of the present invention;
fig. 2 is a graph showing the adsorption effect of tetracycline hydrochloride on the sewage treatment membranes prepared in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment and the fifth embodiment of the present invention;
fig. 3 is a graph showing the effect of the sewage treatment membranes prepared in example one, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 on dynamically adsorbing the tetracycline hydrochloride aqueous solution.
FIG. 4 is a graph of the regeneration-adsorption performance of sample 1 prepared in example one under different conditions; wherein, fig. 4 (a) is regeneration-adsorption performance in the absence of light and in the absence of hydrogen peroxide, fig. 4 (b) is regeneration-adsorption performance in the presence of light and hydrogen peroxide, fig. 4 (c) is regeneration-adsorption performance in the presence of light and in the absence of hydrogen peroxide, and fig. 4 (d) is regeneration-adsorption performance in the absence of light and in the presence of hydrogen peroxide;
fig. 5 is a graph of adsorption effect of dye and antibiotic on a dynamic state of a sewage treatment membrane prepared in the first embodiment, wherein fig. 5 (a) is a graph of adsorption effect of the sewage treatment membrane on the dye, and fig. 5 (b) is a graph of adsorption effect of the sewage treatment membrane on the antibiotic; the dye comprises rhodamine RhB, methyl orange MO and methylene blue MB, and the antibiotic comprises ciprofloxacin CIP, tetracycline hydrochloride TC and oxytetracycline hydrochloride OTC.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of a sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics is characterized by comprising the following steps: the method comprises the following steps:
s1) preparing a metal organic framework material;
s2) dispersing the metal organic framework material and titanium dioxide in N, N-dimethylformamide, uniformly mixing, adding polyvinylidene fluoride and polyvinylpyrrolidone, and stirring in a water bath for a period of time to obtain a casting solution;
and S3) after the membrane casting solution is subjected to ultrasonic defoaming treatment, preparing a membrane by adopting a phase inversion method to obtain the sewage treatment membrane (CFT/PVDF).
Specifically, the metal organic framework material is metal organic framework material MIL-101 (Co, fe) or metal organic framework material MIL-101 (Fe).
Specifically, the preparation method of the metal organic framework material MIL-101 (Co, fe) comprises the following steps:
dissolving cobalt dichloride hexahydrate, ferric trichloride hexahydrate and 2-amino terephthalic acid in N, N-dimethylformamide, uniformly mixing, reacting at 110 ℃ for 20 hours, cooling to room temperature, collecting precipitate, and drying to obtain the powdery metal organic framework material MIL-101 (Co, fe).
Specifically, the mass ratio of cobalt dichloride hexahydrate, ferric trichloride hexahydrate, 2-amino terephthalic acid and N, N-dimethylformamide is 1.
Specifically, the mass ratio of the metal organic framework material powder to the titanium dioxide powder to the N, N-dimethylformamide to the polyvinylidene fluoride to the polyvinylpyrrolidone is (1-2) to (3-4) to 47 (1.5-2.5).
Specifically, the heating temperature of the water bath is 50-80 ℃, and the stirring is carried out for 3-6h under the water bath.
Specifically, the heating temperature of the water bath is 60 ℃, and the stirring is carried out for 5 hours under the water bath.
Specifically, the film preparation process by the phase inversion method comprises the following steps: taking a proper amount of membrane casting liquid on a glass plate, scraping to form a membrane, standing at room temperature for 2-5min, immersing in deionized water at room temperature to form a membrane, and then placing the membrane in new deionized water to be immersed for 10-20h for later use.
Specifically, the thickness of the sewage treatment membrane is 100-300 μm.
Specifically, the thickness of the sewage treatment membrane is 200 μm.
The invention also provides a sewage treatment membrane obtained based on the preparation method of the sewage treatment membrane with the efficient dynamic adsorption and photo-Fenton regeneration characteristics.
The invention also provides application of the sewage treatment membrane in high-efficiency dynamic adsorption of various organic pollutants (dyes and antibiotics) in a water body.
According to the sewage treatment membrane provided by the invention, the metal organic framework material MIL-101 (Co, fe) and titanium dioxide are uniformly distributed on the surface and inside of the polyvinylidene fluoride membrane, the metal organic framework material MIL-101 (Co, fe) effectively improves the pore-forming rate of the obtained sewage treatment membrane, the adsorption performance is enhanced by the synergistic effect of bimetal, the titanium dioxide provides the light regeneration performance, and the MIL-101 (Co, fe) endows the sewage treatment membrane with the light-Fenton regeneration performance, so that the obtained sewage treatment membrane has the characteristic of efficiently adsorbing organic pollutants and the good light-Fenton regeneration characteristic.
Example one
Preparation of a Sewage treatment Membrane (sample 1)
101 Dissolving 0.12g of cobalt dichloride hexahydrate, 1.20g of ferric trichloride hexahydrate and 0.48g of 2-amino terephthalic acid in 30mL of N, N-dimethylformamide, stirring for 30min, transferring to a reaction kettle, reacting at 110 ℃ for 20h, cooling to room temperature, collecting precipitate, washing and drying to obtain a powdery metal organic framework material MIL-101 (Co, fe);
102 0.10g of metal organic framework material MIL-101 (Co, fe) and 0.30g of titanium dioxide are weighed, 0.10g of metal organic framework material MIL-101 (Co, fe) and 0.30g of titanium dioxide are added into N, N-dimethylformamide, magnetic stirring is carried out for 20min at room temperature, 0.85g of polyvinylidene fluoride and 0.25g of polyvinylpyrrolidone are added, and after water bath stirring is carried out for 5h at 60 ℃, a uniformly mixed casting solution is obtained;
103 Carrying out ultrasonic defoaming treatment on the casting solution, carrying out ultrasonic treatment for 20min, removing bubbles in the casting solution, taking a proper amount of the casting solution on a clean glass plate, scraping to form a film, standing at room temperature for 2min, and then soaking in a coagulating bath (deionized water) at room temperature to form the film. The membrane was then soaked in fresh deionized water for 15h to obtain a sewage treatment membrane, sample 1 being labeled CFT/PVDF.
The thickness of sample 1 was 200 μm, and the effective membrane area was 12.56cm 2 。
Example two
The present embodiment is an improvement on the basis of the first embodiment, and details of the first embodiment are not described again.
EXAMPLE III
The present embodiment is an improvement on the basis of the first embodiment, and details of the first embodiment are not described again.
Example four
The present embodiment is an improvement on the basis of the first embodiment, and details of the first embodiment are not described again.
EXAMPLE five
The present embodiment is an improvement on the basis of the first embodiment, and details of the first embodiment are not described herein again.
Preparation of comparative example 1
Comparative example 1 differs from sample 1 in that the amounts of the metal organic framework material MIL-101 (Co, fe) and titanium dioxide powder added were both 0g, and comparative example 1 was obtained and labeled PVDF.
Preparation of comparative example 2
Comparative example 2 differs from sample 1 in that the organic framework material was added in an amount of 0g, resulting in comparative example 2, labeled as TiO 2 /PVDF。
Preparation of comparative example 3
Comparative example 3 differs from sample 1 in that the titanium dioxide was added in an amount of 0g each, resulting in comparative example 3, labeled MIL-101 (Co, fe)/PVDF.
Preparation of comparative example 4
Comparative example 4 differs from sample 1 in that cobalt dichloride hexahydrate was replaced by an equivalent amount of ferric trichloride hexahydrate in the preparation of metal organic framework material MIL-101 (Co, fe); the amount of titanium dioxide powder added was 0g, and comparative example 4, labeled MIL-101 (Fe)/PVDF, was obtained.
Preparation of comparative example 5
Comparative example 5 differs from sample 1 in that in the preparation of metal organic framework material MIL-101 (Co, fe), cobalt dichloride hexahydrate was replaced by an equal amount of iron trichloride hexahydrate, comparative example 5 was obtained, labelled FT/PVD.
As shown in fig. 1, the sample 1 was subjected to morphology analysis by scanning electron microscopy, which indicated that MIL-101 (Co, fe) and titanium dioxide were uniformly distributed in the polyvinylidene fluoride film.
Application of membrane for treating sewage 1
The testing step of the dynamic adsorption tetracycline hydrochloride aqueous solution of the sewage treatment membrane comprises the following steps:
(1) Preparation of 20 mg. L -1 Tetracycline hydrochloride in water, using an ultraviolet spectrophotometerDetermining the light absorption value of the original solution;
(2) Taking a membrane, placing on a self-made dynamic membrane-passing device, and pouring 50mL of 20 mg.L into the device -1 The tetracycline hydrochloride aqueous solution is subjected to dynamic membrane adsorption;
(3) Taking the solution after the membrane passes, and measuring a light absorption value; among them, the characteristic absorption wavelength of tetracycline hydrochloride is 357nm.
Fig. 2 is a graph showing the adsorption effect of sample 1, sample 2, sample 3, sample 4 and sample 5 on tetracycline hydrochloride, and the test results in fig. 2 (a) show that: sample 1, sample 2 and sample 3 all had better adsorption of tetracycline hydrochloride due to the combined effect of MIL-101 (Co, fe) and membrane porosity. Among them, sample 1 had the best adsorption effect, and the adsorption value reached 74.6%. From the test results of fig. 2 (b), it can be seen that: the adsorption effect of sample 4 on tetracycline hydrochloride was poor at a film thickness of 100 μm, while the adsorption effects of sample 5 and sample 1 were not much different at film thicknesses of 200 μm and 300 μm, but the optimum film thickness was selected to be 200 μm from the viewpoint of cost.
Fig. 3 is a graph showing the effect of the sewage treatment membranes prepared in example one, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 in dynamically adsorbing the tetracycline hydrochloride aqueous solution, and the sample 1 prepared in example one has the best adsorption effect on tetracycline hydrochloride, and the adsorption value reaches 74.6%. The adsorption performance of the membrane obtained in comparative example 1 on tetracycline hydrochloride is the worst, and the adsorption performance of the other four membranes on tetracycline hydrochloride is between the two.
Application of sewage treatment membrane 2
Example one the prepared membrane for wastewater treatment (sample 1) was used for photo-Fenton regeneration, photocatalytic regeneration and Fenton reaction regeneration, respectively.
The regeneration-adsorption performance test step of the sewage treatment membrane under the conditions of illumination and hydrogen peroxide comprises the following steps:
(1) Preparation of 20 mg. L -1 Measuring the light absorption value of the original solution by using an ultraviolet spectrophotometer in the aqueous solution of tetracycline hydrochloride;
(2) Taking a membrane, mounting on a self-made dynamic membrane-passing device, and pouring 50mL of 20 mg.L into the device -1 The solution of tetracycline hydrochloride in water is prepared,carrying out dynamic membrane adsorption; and taking the solution after the membrane is passed, and measuring the light absorption value.
(3) For regeneration of the membrane, a certain volume of aqueous solution containing 10-20mM hydrogen peroxide is poured into the device for membrane treatment, and simultaneously xenon lamp is used for irradiation for 60-120min. (light intensity 200mW/cm 2 )
(4) After regeneration, 50mL of 20mg.L was poured into the apparatus -1 Performing dynamic membrane adsorption on tetracycline hydrochloride aqueous solution; and taking the solution after the membrane is passed, and measuring the light absorption value.
(5) The operations of (3) and (4) are repeated two more times.
The operation of photocatalytic regeneration and Fenton reaction regeneration is similar to that described above.
Fig. 4 shows the regeneration-adsorption performance of sample 1 prepared in example one under different conditions, wherein fig. 4 (a) shows the regeneration-adsorption performance in the absence of light and in the absence of hydrogen peroxide, fig. 4 (b) shows the regeneration-adsorption performance in the presence of light and in the presence of hydrogen peroxide, fig. 4 (c) shows the regeneration-adsorption performance in the presence of light but without hydrogen peroxide, and fig. 4 (d) shows the regeneration-adsorption performance in the absence of light but with hydrogen peroxide; the results in fig. 4 show that the membrane of fig. 4 (a) that was not regenerated by light or Fenton undergoes a second adsorption, the adsorption performance is significantly reduced; the larger the number of times of adsorption, the worse the adsorption performance. Both the photocatalytic regeneration and the Fenton reaction regeneration of FIGS. 4 (c) and 4 (d) have certain effects; the effect of the light-Fenton synergistic regeneration shown in FIG. 4 (b) is best, and the regeneration efficiency is close to 90%.
Application of sewage treatment membrane 3
The membrane for wastewater treatment (sample 1) prepared in the first example was applied to treat various dyes and various antibiotics, respectively.
(1) Preparation of 10 mg. L -1 Or 20 mg.L of the dye solution -1 The light absorption value of the original solution is measured by an ultraviolet spectrophotometer;
(2) A membrane is arranged on a self-made dynamic membrane passing device, 50mL of dye or antibiotic aqueous solution is poured into the device, and dynamic membrane passing adsorption is carried out;
(3) And taking the solution after the membrane is passed, and measuring the light absorption value.
Fig. 5 is a graph of adsorption effect of dye and antibiotic on a dynamic state of a sewage treatment membrane prepared in the first embodiment, wherein fig. 5 (a) is a graph of adsorption effect of the sewage treatment membrane on the dye, and fig. 5 (b) is a graph of adsorption effect of the sewage treatment membrane on the antibiotic; the dye comprises rhodamine RhB, methyl orange MO and methylene blue MB, and the antibiotic comprises ciprofloxacin CIP, tetracycline hydrochloride TC and oxytetracycline hydrochloride OTC; from the results shown in fig. 5, it can be seen that: the sample 1 has excellent adsorption effect on the dye, and the adsorption performance is close to 100%. The sample 1 has good adsorption effect on antibiotics, and the adsorption performance is over 70%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics is characterized by comprising the following steps: the method comprises the following steps:
preparing a metal organic framework material;
dispersing a metal organic framework material and titanium dioxide in N, N-dimethylformamide, uniformly mixing, adding polyvinylidene fluoride and polyvinylpyrrolidone, and stirring in a water bath for a period of time to obtain a casting solution;
and (3) after the membrane casting solution is subjected to ultrasonic defoaming treatment, preparing a membrane by adopting a phase inversion method to obtain a sewage treatment membrane (CFT/PVDF).
2. The method for preparing a sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics according to claim 1, wherein the method comprises the following steps: the metal organic framework material is metal organic framework material MIL-101 (Co, fe) or metal organic framework material MIL-101 (Fe).
3. The method for preparing a sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics according to claim 2, wherein the method comprises the following steps: the preparation method of the metal organic framework material MIL-101 (Co, fe) comprises the following steps:
dissolving cobalt dichloride hexahydrate, ferric trichloride hexahydrate and 2-amino terephthalic acid in N, N-dimethylformamide, uniformly mixing, reacting at 110 ℃ for 20 hours, cooling to room temperature, collecting precipitate, and drying to obtain the powdery metal organic framework material MIL-101 (Co, fe).
4. The method for preparing the sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics according to claim 3, wherein the method comprises the following steps: the mass ratio of the cobalt dichloride hexahydrate to the ferric trichloride hexahydrate to the 2-amino terephthalic acid to the N, N-dimethylformamide is 1.
5. The method for preparing a sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics according to claim 1, wherein the method comprises the following steps: the mass ratio of the metal organic framework material powder to the titanium dioxide powder to the N, N-dimethylformamide to the polyvinylidene fluoride to the polyvinylpyrrolidone is (1-2) to (3-4) and is (1.5-2.5).
6. The method for preparing a sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics according to claim 1, wherein the method comprises the following steps: heating in water bath at 50-80 deg.C, and stirring in water bath for 3-6 hr.
7. The method for preparing the sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics according to claim 1, wherein the method comprises the following steps: the film making process by the phase inversion method comprises the following steps: taking a proper amount of membrane casting liquid on a glass plate, scraping to form a membrane, standing at room temperature for 2-5min, immersing in deionized water at room temperature to form a membrane, and then placing the membrane in new deionized water to be immersed for 10-20h for later use.
8. The method for preparing the sewage treatment membrane with high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics according to claim 1, wherein the method comprises the following steps: the thickness of the sewage treatment membrane is 100-300 mu m.
9. A sewage treatment membrane obtained based on the sewage treatment membrane preparation method having high-efficiency dynamic adsorption and photo-Fenton regeneration characteristics as claimed in any one of claims 1 to 8.
10. Use of a membrane for the treatment of water according to claim 9 for the highly efficient dynamic adsorption of a plurality of organic pollutants (dyes, antibiotics) in a body of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210823897.2A CN115178110B (en) | 2022-07-13 | 2022-07-13 | Sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210823897.2A CN115178110B (en) | 2022-07-13 | 2022-07-13 | Sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115178110A true CN115178110A (en) | 2022-10-14 |
| CN115178110B CN115178110B (en) | 2024-01-30 |
Family
ID=83520040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210823897.2A Active CN115178110B (en) | 2022-07-13 | 2022-07-13 | Sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115178110B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498553A (en) * | 2015-12-11 | 2016-04-20 | 华南理工大学 | Polyvinylidene fluoride and metal-organic framework composite ultra-filtration membrane and preparation and application |
| CN106238100A (en) * | 2016-07-28 | 2016-12-21 | 北京科技大学 | The preparation of titanium dioxide nanoplate load MIL 100 (Fe) composite photocatalyst material and application process |
| CN107913673A (en) * | 2017-10-27 | 2018-04-17 | 清华大学 | A kind of metal-organic framework materials and its method for removal water body organic drug pollution |
| JP2019018178A (en) * | 2017-07-20 | 2019-02-07 | 旭化成株式会社 | Separation membrane |
| CN109603762A (en) * | 2018-12-27 | 2019-04-12 | 南京大学 | A kind of adsorbed film based on metal-organic framework materials, preparation method and application |
| CN110882725A (en) * | 2019-12-06 | 2020-03-17 | 北京科技大学 | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof |
| CN111530504A (en) * | 2020-05-11 | 2020-08-14 | 深圳市臻鼎环保科技有限公司 | Photocatalytic sewage treatment membrane and preparation method thereof |
| WO2022021051A1 (en) * | 2020-07-28 | 2022-02-03 | 湖南大学 | Quantum dot-modified metal organic framework photocatalyst, preparation method therefor and application thereof |
-
2022
- 2022-07-13 CN CN202210823897.2A patent/CN115178110B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498553A (en) * | 2015-12-11 | 2016-04-20 | 华南理工大学 | Polyvinylidene fluoride and metal-organic framework composite ultra-filtration membrane and preparation and application |
| CN106238100A (en) * | 2016-07-28 | 2016-12-21 | 北京科技大学 | The preparation of titanium dioxide nanoplate load MIL 100 (Fe) composite photocatalyst material and application process |
| JP2019018178A (en) * | 2017-07-20 | 2019-02-07 | 旭化成株式会社 | Separation membrane |
| CN107913673A (en) * | 2017-10-27 | 2018-04-17 | 清华大学 | A kind of metal-organic framework materials and its method for removal water body organic drug pollution |
| CN109603762A (en) * | 2018-12-27 | 2019-04-12 | 南京大学 | A kind of adsorbed film based on metal-organic framework materials, preparation method and application |
| CN110882725A (en) * | 2019-12-06 | 2020-03-17 | 北京科技大学 | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof |
| CN111530504A (en) * | 2020-05-11 | 2020-08-14 | 深圳市臻鼎环保科技有限公司 | Photocatalytic sewage treatment membrane and preparation method thereof |
| WO2022021051A1 (en) * | 2020-07-28 | 2022-02-03 | 湖南大学 | Quantum dot-modified metal organic framework photocatalyst, preparation method therefor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115178110B (en) | 2024-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20200024162A1 (en) | Method and device for sewage treatment | |
| GB2582681A (en) | Method and device for sewage treatment | |
| CN106669621B (en) | A kind of preparation method and application of chitosan/zeolite adsorbent | |
| WO2021093832A1 (en) | C3n4 modified organic film preparation method and application | |
| CN102580746A (en) | Activated carbon supported cobalt oxide catalyst and application of same in organic pollutant degradation | |
| CN102616881A (en) | Treatment process for printing and dyeing wastewater | |
| CN104528912B (en) | A kind of photocatalysis apparatus based on nano-magnetic titanium deoxide catalyst | |
| CN112156662B (en) | Self-cleaning electrostatic spinning nanofiber filter membrane, preparation method and application | |
| CN106512988B (en) | A kind of molecular sieve carried type MnO2- ZnO ozone catalyst and preparation method thereof | |
| CN115193469B (en) | Preparation method, application and water treatment method of photocatalytic ceramic membrane | |
| CN109046368B (en) | Coal chemical wastewater deep oxidation catalyst and preparation method thereof | |
| CN108607583A (en) | A kind of carbon-based oxyhalogen bismuth composite catalyst of photocatalytic degradation volatile organic matter and its preparation method and application | |
| CN104329741A (en) | Indoor photocatalysis air purifier and purification method | |
| CN115178110A (en) | Sewage treatment membrane with efficient dynamic adsorption and photo-Fenton regeneration characteristics as well as preparation method and application thereof | |
| CN114702097B (en) | Immersed coupling membrane filtration reactor, preparation method and application thereof | |
| Wang et al. | Catalytic ceramic membrane integrated with granular activated carbon for efficient removal of organic pollutants | |
| CN108083517B (en) | Integrated purification process for heavy metal wastewater | |
| CN104826432A (en) | Composite air purification method | |
| CN102120665B (en) | Method for purifying pentachlorophenol in water through photocatalysis | |
| CN201785291U (en) | Contact oxidation and sand filtration integrated processing system for light polluted water treatment | |
| CN108607521A (en) | A kind of modified oxidized aluminium base scavenging material and preparation method thereof except formaldehyde | |
| CN114832783A (en) | Adsorbing material, preparation method and cleaning method | |
| CN111514859B (en) | Composite adsorbent for efficiently removing mixed pollutants in wastewater and preparation method thereof | |
| CN112973796A (en) | Catalyst for quickly and efficiently degrading methylene blue wastewater and preparation method and application thereof | |
| CN112718001A (en) | Nano cellulose based aerogel composite photocatalyst and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |