CN115283013A - Preparation method of nano manganese dioxide organic catalytic membrane - Google Patents
Preparation method of nano manganese dioxide organic catalytic membrane Download PDFInfo
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- CN115283013A CN115283013A CN202211057213.9A CN202211057213A CN115283013A CN 115283013 A CN115283013 A CN 115283013A CN 202211057213 A CN202211057213 A CN 202211057213A CN 115283013 A CN115283013 A CN 115283013A
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000012528 membrane Substances 0.000 title claims abstract description 118
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005266 casting Methods 0.000 claims abstract description 42
- 238000007790 scraping Methods 0.000 claims abstract description 22
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 50
- 239000010410 layer Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 25
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- 239000000843 powder Substances 0.000 claims description 18
- 239000003344 environmental pollutant Substances 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
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- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
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- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
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- 238000005086 pumping Methods 0.000 claims description 3
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
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- 231100000719 pollutant Toxicity 0.000 description 10
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 5
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- 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
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 3
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- 150000003254 radicals Chemical class 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 229920001007 Nylon 4 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000012286 potassium permanganate Substances 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
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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
- C02F1/72—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
-
- 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
- C02F2101/345—Phenols
-
- 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
Abstract
A method for preparing a nano manganese dioxide organic catalytic membrane. The invention relates to a preparation method of a nano manganese dioxide organic catalytic membrane. The invention aims to solve the problems that the catalyst has low mass transfer efficiency, is not easy to separate and recover and the existing ultrafiltration membrane has poor effect of removing the organic pollutants which are difficult to degrade. The method comprises the following steps: 1. preparing manganese dioxide membrane casting liquid; 2. preparing a supporting layer membrane casting solution; 3. respectively standing the manganese dioxide membrane casting solution and the supporting layer membrane casting solution for defoaming to obtain the defoamed manganese dioxide membrane casting solution and the defoamed supporting layer membrane casting solution; and (3) carrying out one-step in-situ film scraping by using a double-head film scraping knife, and immersing the film into water for phase conversion to obtain the nano manganese dioxide organic catalytic film. The method is used for catalyzing persulfate to remove organic micropollutants difficult to degrade.
Description
Technical Field
The invention relates to a preparation method of a nano manganese dioxide organic catalytic membrane.
Background
With the acceleration of the urbanization process, the emergence of new pollutants in sewage treatment systems has attracted people's attention. Emerging pollutants include medicines and personal care products, endocrine disruptors and the like, have high biological activity and toxicity, and bring serious negative effects on human health and ecological environment. These emerging dissolved pollutants are difficult to treat by a single physicochemical or biochemical process, and finding other effective means to treat these toxic and nonbiodegradable organics is a primary concern today.
Various methods for treating trace contaminants have been developed including biological, physical and advanced oxidation methods. The emerging advanced oxidation technology has wide application in the aspect of treating trace pollutants due to the characteristics of high efficiency, high reaction speed, thoroughness, simple operation and the like. The traditional oxidation technologies such as ozone, hydrogen peroxide and potassium permanganate applied to the degradation of organic matters in sewage have the problems of high toxicity, poor treatment effect and the like. Compared with the traditional method, the persulfate advanced oxidation technology has higher oxidation efficiency, stronger stability and lower cost, is commonly used for the treatment of sewage disinfection, organic sewage, heavy metal sewage and the like, and has good application prospect. Persulfate can be ionized in water to form peroxodisulfate ion (S) 2 O 8 2- )，S 2 O 8 2- Under the action of external activation, the double oxygen bond is broken to generate sulfate radical free radical which has strong oxidizing ability. The heterogeneous catalysis persulfate oxidation technology is a hotspot in the field of water treatment in recent years, and is characterized in that a solid catalyst is introduced into a reaction system on the basis of persulfate oxidation, and the catalyst can react with persulfate dissolved in water to accelerate the decomposition of an oxidant and generate a large amount of active free radicals with strong oxidizing capacity, so that the oxidation removal efficiency of organic pollutants is improved. Currently, many persulfate-activating catalysts including heat, transition metal ions, ultraviolet light, carbon materials, metal oxides, ultrasound and the like are researched, and it is very important to find a high-efficiency, stable and environment-friendly catalyst. The manganese oxide has good catalytic activity, low price, abundance, easy obtaining and environment-friendly property. Among them, manganese dioxide is an excellent multifunctional nano material, and has been widely used in recent years due to its high environmental compatibility. However, the heterogeneous catalyst system has the disadvantages of low mass transfer efficiency, difficult separation and recovery, and the like, thereby reducing the catalytic activity sites in the catalytic oxidation reaction.
The membrane filtration technology is an important component in the advanced treatment technology of drinking water, wherein the ultrafiltration membrane separation technology and the combined technology thereof meet the requirement of continuously improving the water quality of the drinking water, and realize large-scale and industrialized application in drinking water plants in cities and towns in China. As a substitute product of the traditional drinking water treatment process, the ultrafiltration can effectively retain suspended matters, colloids, macromolecular organic matters, microorganisms and other impurities in water, and plays an important barrier role in the safety guarantee of the drinking water quality. Despite the advantages of ultrafiltration, the major functions of ultrafiltration, namely pore size sieving and retention, are not effective in meeting the treatment requirements of emerging organic pollutants, which has become the focus of increasing attention. Therefore, it is important to enhance the versatility of current film materials.
Disclosure of Invention
The invention provides a preparation method of a nano manganese dioxide organic catalytic membrane, aiming at solving the problems that the catalyst is low in mass transfer efficiency and difficult to separate and recover and the existing ultrafiltration membrane is poor in effect of removing organic pollutants difficult to degrade.
The preparation method of the nano manganese dioxide organic catalytic membrane comprises the following steps:
1. adding manganese dioxide nanoparticles, a pore-forming agent I and polymer powder I into a solvent I, transferring to a ball milling tank, and carrying out ball milling to obtain a manganese dioxide membrane casting solution; the volume ratio of the mass of the manganese dioxide nano particles to the solvent I is (2.5-20) g (15-42.5) mL; the mass ratio of the pore-foaming agent I to the solvent I is (1-5) g, (15-42.5) mL; the volume ratio of the mass of the polymer powder I to the volume of the solvent I is (4-10) g, (15-42.5) mL;
2. adding polymer powder II and a pore-forming agent II into a solvent II, and stirring to obtain a supporting layer membrane casting solution; the volume ratio of the mass of the polymer powder II to the volume of the solvent II is (16-26) g (64-81) mL; the volume ratio of the mass of the pore-foaming agent II to the solvent II is (3-10) g (64-81) mL;
3. respectively standing the manganese dioxide membrane casting solution and the supporting layer membrane casting solution for defoaming to obtain a defoamed manganese dioxide membrane casting solution and a defoamed supporting layer membrane casting solution; and (3) carrying out one-step in-situ film scraping by using a double-head film scraping knife, and immersing the film into water for phase conversion to obtain the nano manganese dioxide organic catalytic film.
The invention has the beneficial effects that:
the preparation process of the nano organic catalytic membrane prepared by the invention is simple, the industrial flow line production is easy, and the product is stable.
The material used in the preparation method can not generate secondary pollution, and the catalysis-filtration process has mild conditions and does not need additional energy such as light, heat or ultrasound.
The regular nano-pore channels provided by the membrane provide opportunities for uniform loading of the catalyst, expose more active sites and provide larger specific surface area. Meanwhile, the unique property of the catalyst can improve the surface hydrophilicity of the membrane and enhance the mechanical strength of the membrane. The method solves the problems of low mass transfer efficiency of the catalyst and difficult separation and recovery, and simultaneously realizes the improvement of the pollution resistance and the mechanical property of the membrane. The method not only provides an implementable solution for the efficient degradation of organic trace pollutants in the water body, but also widens the application range of the water treatment ultrafiltration membrane, and has wide market prospect.
Drawings
FIG. 1 is a schematic diagram of a cross-flow membrane filtration-catalytic oxidation unit;
FIG. 2 is a bar graph of the effect of the nano manganese dioxide organic catalytic film on the atrazine;
FIG. 3 is a graph comparing the treatment effect of the nano manganese dioxide organic catalytic film on other types of organic pollutants;
FIG. 4 is an identification diagram of active species of a nano manganese dioxide organic catalytic membrane reaction system;
FIG. 5 is a schematic view of a one-step in-situ film wiping process using a double-ended doctor blade;
FIG. 6 is a schematic structural view of a double-head doctor blade;
fig. 7 is a side view of a double-ended doctor blade.
Detailed Description
The first embodiment is as follows: the preparation method of the nano manganese dioxide organic catalytic membrane in the embodiment is carried out according to the following steps:
1. adding manganese dioxide nanoparticles, a pore-forming agent I and polymer powder I into a solvent I, transferring to a ball milling tank, and carrying out ball milling to obtain a manganese dioxide membrane casting solution; the volume ratio of the mass of the manganese dioxide nano particles to the solvent I is (2.5-20) g (15-42.5) mL; the volume ratio of the mass of the pore-foaming agent I to the solvent I is (1-5) g (15-42.5) mL; the volume ratio of the mass of the polymer powder I to the volume of the solvent I is (4-10) g, (15-42.5) mL;
2. adding the polymer powder II and the pore-forming agent II into the solvent II, and stirring to obtain a supporting layer membrane casting solution; the volume ratio of the mass of the polymer powder II to the volume of the solvent II is (16-26) g, (64-81) mL; the volume ratio of the mass of the pore-foaming agent II to the solvent II is (3-10) g (64-81) mL;
3. respectively standing the manganese dioxide membrane casting solution and the supporting layer membrane casting solution for defoaming to obtain the defoamed manganese dioxide membrane casting solution and the defoamed supporting layer membrane casting solution; and (3) carrying out one-step in-situ film scraping by using a double-head film scraping knife, and immersing the film into water for phase inversion to obtain the nano manganese dioxide organic catalytic film.
Polymer powder I in this embodimentAndthe polymer powder II is dried in a vacuum drying oven at 60 ℃ for standby before use.
In the embodiment, the nano manganese dioxide organic catalytic membrane with the manganese dioxide catalytic functional layer and the membrane separation layer is realized by one-step in-situ co-casting of the manganese dioxide membrane casting solution and the polymer membrane casting solution. The treatment system takes persulfate as an oxidant, and when feed liquid injected with persulfate passes through the manganese dioxide organic catalytic membrane under the driving of pressure, active species with strong oxidizing capability can be generated, and then the active species react with organic pollutants in water, so that the purpose of degrading the pollutants is achieved. Compared with the liquid phase catalysis mode, the nano catalytic membrane catalysis system has the idea of performing reaction in a nano space, so that the distance between the target organic pollutant and the active free radical with short service life is kept in a certain range. According to Fick's law, the strategy can effectively improve the mass transfer between the persulfate oxidant and the heterogeneous catalyst, thereby improving the activation efficiency of manganese dioxide. From the aspect of the membrane, the abundant hydroxyl groups on the surface of the nano manganese dioxide are beneficial to the improvement of the membrane performance, and are mainly reflected in the anti-pollution performance. Meanwhile, part of chemical bonds of the nano manganese dioxide can be used as cross-linking points to connect polymer chains, so that an organic-inorganic network structure is formed, and the mechanical property of the film is improved. The addition of nano manganese dioxide allows the membrane to exhibit excellent separation function.
In the embodiment, the domain-limited effect of the manganese dioxide organic catalytic membrane is utilized to catalyze persulfate to degrade organic pollutants, so that the mass transfer diffusion of the pollutants and the oxidant to the surface of the manganese dioxide catalyst through the nano-pore channels is enhanced under the action of the nano-domain limit, active oxygen free radicals can be rapidly generated, and the pollutants can be efficiently and rapidly degraded. Compared with the common dispersed catalysis mode, the catalyst has higher catalysis efficiency. Meanwhile, the manganese dioxide catalyst supplements the defects of the existing ultrafiltration membrane, has a powerful catalytic function and can fully realize the improvement of the pollution resistance and the mechanical property of the membrane. The reaction process constructed by the invention has the advantages of high efficiency, environmental protection, small occupied area, easy modularization, easy expansion and the like.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: and the ball milling in the step one is carried out for 72 hours at room temperature. Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in step two, the stirring is performed at 60 ℃ for 24 hours by mechanical stirring. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: the polymer powder I is polyvinylidene fluoride, polytetrafluoroethylene, polyether sulfone or polypropylene; the polymer powder II is polyvinylidene fluoride, polytetrafluoroethylene, polyether sulfone or polypropylene. Other steps and parameters are the same as those in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the solvent I is one or a combination of more of N, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide; the solvent II is one or a combination of more of N, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the pore-foaming agent I is one or a combination of more of polyvinylpyrrolidone, ethanol, polyethylene glycol and glycerol; the pore-forming agent II is one or a combination of more of polyvinylpyrrolidone, ethanol, polyethylene glycol and glycerol. Other steps and parameters are the same as those in one of the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: step three, carrying out one-step in-situ film scraping by using a double-head film scraping knife specifically comprises the following steps:
placing the non-woven fabric on a clean glass plate, pouring the foam-removed manganese dioxide membrane casting solution on the left side of the non-woven fabric, pouring the foam-removed supporting layer membrane casting solution on the right side of the foam-removed manganese dioxide membrane casting solution, scraping a double-layer solution membrane from left to right by using a double-head membrane scraping knife, and then standing in the air for 20s; the thickness of the support layer in the two-layer solution film was 150 μm, and the thickness of the coating layer was 50 μm. Other steps and parameters are the same as those in one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the step three, immersing in water for phase inversion, is specifically carried out according to the following steps:
putting the double-layer solution film and the glass plate into a coagulating bath at 22 ℃ for 36h, and replacing the coagulating bath for at least 3 times to obtain a cured film; soaking the cured film in deionized water to eliminate organic solvent, tearing off the film and storing in refrigerator at 4 deg.c. Other steps and parameters are the same as those in one of the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the double-end film scraping knife comprises a knife support 1 and two scrapers 2, wherein the knife support 1 comprises two right-angle trapezoidal side plates 3 and two cross beams 4 transversely arranged on the two right-angle trapezoidal side plates 3, the bottoms of the two right-angle trapezoidal side plates 3 are transversely provided with a knife fixing cylindrical cross rod 5, and the two scrapers 2 are respectively embedded in the knife support 1; the double-end knifes still include thick adjusting device of membrane, thick adjusting device of membrane including hanging down and locating four screw micrometer subassembly 6 of scraper 2, four screw micrometer subassembly 6 wear to establish on scraper 2, every screw micrometer subassembly 6 passes through the spring and links to each other with scraper 2. Other steps and parameters are the same as those in one to eight of the embodiments.
The scraper fixing cylindrical cross rod 5 transversely arranged at the bottom of the right trapezoid side plate is pulled to drive the whole double-end film scraping cutter to move transversely, so that the scraper scrapes films.
The specific implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is that: the nano manganese dioxide organic catalytic film obtained in the third step is used for catalyzing persulfate to remove organic micropollutants difficult to degrade; specifically, mixing an organic micro-pollutant solution with a persulfate stock solution, and filtering by pumping into a cross-flow filtering device provided with a nano manganese dioxide organic catalytic membrane; the persulfate stock solution is potassium hydrogen persulfate, ammonium persulfate or sodium persulfate, the concentration of the persulfate stock solution is 100mmol/L, the concentration of the organic micro-pollutant solution is 50 mu mol/L-500 mmol/L, the pressure of the pumped membrane filter is 0.1-0.5 MPa, and the flow rate of the pumped membrane filter is 0.1-10 mL/min. Other steps and parameters are the same as those in one of the first to ninth embodiments.
The following examples were employed to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the nano manganese dioxide organic catalytic membrane comprises the following steps:
1. adding 10g of manganese dioxide nanoparticles, 3g of polyvinylpyrrolidone and 6g of polyvinylidene fluoride into 31mLN-N dimethylformamide, and transferring to a ball milling tank for ball milling to obtain a manganese dioxide casting solution;
2. adding 22g of polyvinylidene fluoride and 3g of polypyrrolidone into 75mLN-N dimethylformamide, and stirring to obtain a supporting layer casting solution;
3. respectively standing the manganese dioxide membrane casting solution and the supporting layer membrane casting solution for defoaming to obtain the defoamed manganese dioxide membrane casting solution and the defoamed supporting layer membrane casting solution; placing the non-woven fabric on a clean glass plate, pouring the foam-removed manganese dioxide membrane casting solution on the left side of the non-woven fabric, pouring the foam-removed supporting layer membrane casting solution on the right side of the foam-removed manganese dioxide membrane casting solution, scraping a double-layer solution membrane from left to right by using a double-head membrane scraping knife, and then standing in the air for 20s; putting the double-layer solution film and the glass plate into a coagulating bath at 22 ℃ for 36h, and replacing the coagulating bath for at least 3 times to obtain a cured film; soaking the cured film in deionized water to remove the organic solvent in the film, finally uncovering the film, and storing in a refrigerator at 4 ℃ to obtain a nano manganese dioxide organic catalytic film; the thickness of the support layer in the two-layer solution film was 150 μm, and the thickness of the coating layer was 50 μm.
Taking organic trace pollutant atrazine as an example, firstly preparing feed liquid with atrazine concentration of 50 mu mol/L, pumping atrazine into a cross flow filter with a nano manganese dioxide organic catalytic membrane by a peristaltic pump under the cross flow filtration mode, wherein the pressure is 0.1MPa, and the membrane adsorption saturation is achieved after the operation for 30 min; then 2mmol/L potassium hydrogen peroxodisulfate was injected into the feed solution, and the operation was continued at a pressure of 0.1MPa for 120min to calculate the degradation efficiency of the contaminants.
Example 2: in order to investigate the catalytic performance (filtration) of the catalytic membrane + potassium hydrogen peroxodisulfate system and to compare the catalytic performance under static conditions (membrane immersed in 250mL atrazine solution containing oxidant, without pressure actuation) using only the oxidant system and the catalytic membrane + oxidant system. As shown in fig. 2, the contribution of physical adsorption of the membrane to overall atrazine removal was negligible, regardless of the original membrane or the nano-manganese dioxide catalyzed membrane. The atrazine concentration of the original membrane decreased only slightly under the effect of potassium peroxodisulfate, indicating that the membrane without manganese dioxide coating did not have potassium peroxodisulfate activation capability. Under the catalytic action of the nano manganese dioxide catalytic film, the removal efficiency of 120min is the highest, and is 62.0%. After the treatment with the single oxidant and the catalytic membrane plus oxidant (static state), the degradation efficiency is 2.8% and 9.4% respectively. This clearly demonstrates the superiority of the synergy of oxidation and filtration when the nano manganese dioxide catalytic membrane activates potassium hydrogen peroxydisulfate to remove atrazine. This is because the reactions occurring at the membrane surface and pores enhance the mass transfer diffusion between manganese dioxide and potassium hydrogen peroxydisulfate, thereby promoting effective atrazine removal.
Example 3: in order to objectively evaluate the catalytic performance of the nano manganese dioxide catalytic membrane, the dye methylene blue and three micropollutants, carbamazepine, phenol and paracetamol, are degraded under the same condition. As shown in fig. 3, the removal rate of methylene blue by electrostatic adsorption of the catalytic membrane was 17.7% and 25.6%, respectively. In contrast, the bulk removal of paracetamol, phenol and carbamazepine is dominated by the catalytic degradation of the membrane. Under conditions where adsorption is not a concern. The removal rates of paracetamol, methylene blue, phenol and carbamazepine by the catalytic membrane + potassium hydrogen peroxydisulfate system were 82.6%, 71.9%, 49.6% and 40.1%, respectively. The results show that the nano manganese dioxide catalytic membrane shows catalytic capability and applicability to different organic pollutants in the water treatment process.
Example 4: the active species involved in the catalytic membrane + potassium hydrogen peroxydisulfate system was determined by electron paramagnetic resonance spectroscopy. As shown in fig. 4, no significant peak signal was observed with the oxidizer system alone and the original membrane + oxidizer system. In the catalytic membrane + oxidant system, the characteristic signals of spin adducts of hydroxyl radicals and sulfate radicals are easy to detect. This indicates that the nano manganese dioxide catalytic membrane generates hydroxyl radicals and sulfate radicals during the in-situ activation of potassium hydrogen persulfate. The nano manganese dioxide provides rich active sites for catalyzing potassium hydrogen peroxydisulfate, and pollutants are efficiently removed by virtue of the synergistic effect of limited catalytic oxidation and membrane filtration.
Claims (10)
1. A preparation method of a nano manganese dioxide organic catalytic membrane is characterized by comprising the following steps:
1. adding manganese dioxide nanoparticles, a pore-forming agent I and polymer powder I into a solvent I, transferring to a ball milling tank, and carrying out ball milling to obtain a manganese dioxide membrane casting solution; the volume ratio of the mass of the manganese dioxide nano particles to the solvent I is (2.5-20) g, (15-42.5) mL; the mass ratio of the pore-foaming agent I to the solvent I is (1-5) g, (15-42.5) mL; the volume ratio of the mass of the polymer powder I to the volume of the solvent I is (4-10) g, (15-42.5) mL;
2. adding the polymer powder II and the pore-forming agent II into the solvent II, and stirring to obtain a supporting layer membrane casting solution; the volume ratio of the mass of the polymer powder II to the volume of the solvent II is (16-26) g (64-81) mL; the volume ratio of the mass of the pore-foaming agent II to the solvent II is (3-10) g (64-81) mL;
3. respectively standing the manganese dioxide membrane casting solution and the supporting layer membrane casting solution for defoaming to obtain the defoamed manganese dioxide membrane casting solution and the defoamed supporting layer membrane casting solution; and (3) carrying out one-step in-situ film scraping by using a double-head film scraping knife, and immersing the film into water for phase conversion to obtain the nano manganese dioxide organic catalytic film.
2. The method of claim 1, wherein the ball milling in step one is performed at room temperature for 72h.
3. The method of claim 1, wherein the stirring in step two is performed by mechanical stirring at 60 ℃ for 24 hours.
4. The preparation method of the nano manganese dioxide organic catalytic membrane according to claim 1, wherein the polymer powder I is polyvinylidene fluoride, polytetrafluoroethylene, polyether sulfone or polypropylene; the polymer powder II is polyvinylidene fluoride, polytetrafluoroethylene, polyether sulfone or polypropylene.
5. The method for preparing the nano manganese dioxide organic catalytic membrane according to claim 1, wherein the solvent I is one or a combination of N, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide; the solvent II is one or a combination of more of N, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide.
6. The method for preparing the nano manganese dioxide organic catalytic membrane according to claim 1, wherein the pore-forming agent I is one or a combination of polyvinylpyrrolidone, ethanol, polyethylene glycol and glycerol; the pore-forming agent II is one or a combination of more of polyvinylpyrrolidone, ethanol, polyethylene glycol and glycerol.
7. The preparation method of the nano manganese dioxide organic catalytic membrane according to claim 1, wherein the step three of performing one-step in-situ membrane scraping by using a double-head membrane scraping knife is specifically performed according to the following steps:
placing a non-woven fabric on a clean glass plate, pouring the bubble-removed manganese dioxide membrane casting solution on the left side of the non-woven fabric, pouring the bubble-removed supporting layer membrane casting solution on the right side of the bubble-removed manganese dioxide membrane casting solution, scraping a double-layer solution membrane from left to right by using a double-head membrane scraping knife, and then standing in the air for 20s; the thickness of the support layer in the two-layer solution film was 150 μm, and the thickness of the coating layer was 50 μm.
8. The method for preparing nano manganese dioxide organic catalytic membrane according to claim 1, wherein the step three of immersing in water for phase inversion comprises the following steps:
putting the double-layer solution film and the glass plate into a coagulating bath at 22 ℃ for 36h, and replacing the coagulating bath for at least 3 times to obtain a cured film; soaking the cured film in deionized water to eliminate organic solvent, stripping the film and storing in refrigerator at 4 deg.c.
9. The preparation method of the nano-manganese dioxide organic catalytic membrane according to claim 7, wherein the double-end membrane scraping knife comprises a scraper support (1) and two scrapers (2), the scraper support (1) comprises two right-angle trapezoidal side plates (3) and two cross beams (4) transversely arranged on the two right-angle trapezoidal side plates (3), a scraper fixing cylindrical cross rod (5) is transversely arranged at the bottom of each right-angle trapezoidal side plate (3), and the two scrapers (2) are respectively embedded in the scraper support (1); the double-end knifes of scraping still include thick adjusting device of membrane, thick adjusting device of membrane including hanging down and locating four spiral micrometer module (6) of scraper (2), four spiral micrometer module (6) are worn to establish on scraper (2), every spiral micrometer module (6) link to each other with scraper (2) through the spring.
10. The preparation method of the nano manganese dioxide organic catalytic membrane according to claim 1, wherein the nano manganese dioxide organic catalytic membrane obtained in the third step is used for catalyzing persulfate to remove refractory organic micropollutants; specifically, mixing an organic micro-pollutant solution with a persulfate stock solution, and filtering by pumping into a cross-flow filtering device provided with a nano manganese dioxide organic catalytic membrane; the persulfate stock solution is potassium hydrogen persulfate, ammonium persulfate or sodium persulfate, the concentration of the persulfate stock solution is 100mmol/L, the concentration of the organic micro-pollutant solution is 50 mu mol/L-500 mmol/L, the pressure of the pumped membrane filter is 0.1-0.5 MPa, and the flow rate of the pumped membrane filter is 0.1-10 mL/min.
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