CN115463564B - Modification method for in-situ growth of manganese dioxide on ultrafiltration membrane surface based on metal polyphenol network - Google Patents
Modification method for in-situ growth of manganese dioxide on ultrafiltration membrane surface based on metal polyphenol network Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000012528 membrane Substances 0.000 title claims abstract description 103
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims abstract description 56
- 235000013824 polyphenols Nutrition 0.000 title claims abstract description 56
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 51
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- 238000002715 modification method Methods 0.000 title abstract description 4
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 119
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 119
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 27
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 27
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 18
- 229940033123 tannic acid Drugs 0.000 claims abstract description 18
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 18
- 229920002258 tannic acid Polymers 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 40
- 235000019198 oils Nutrition 0.000 description 40
- 230000014759 maintenance of location Effects 0.000 description 26
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 235000012424 soybean oil Nutrition 0.000 description 7
- 239000003549 soybean oil Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 238000012876 topography Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- 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
-
- 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
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a modification method for manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network in situ, and belongs to the field of membrane material modification. The invention aims to solve the technical problems of low rejection rate of the existing ultrafiltration membrane to emulsified oil and small rejection effect of the membrane surface to emulsified oil pollutants. The modification method comprises the following steps: 1. preparing a tannic acid solution and a manganese acetate solution, mixing to obtain a metal polyphenol network modified solution, and infiltrating a polyethersulfone ultrafiltration membrane; 2. preparing a manganese acetate growth solution, soaking, and then performing hydrothermal reaction; 3. soaking in potassium permanganate solution. The modified organic-inorganic composite membrane has obviously enhanced emulsified oil interception performance, anti-pollution performance and long-term operation stability, improves the treatment effect of the organic ultrafiltration membrane in the application of oily wastewater, and prolongs the service life of the organic ultrafiltration membrane. The ultrafiltration membrane prepared by the invention is applied to the field of oily wastewater treatment.
Description
Technical Field
The invention belongs to the field of membrane material modification, and particularly relates to a method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network.
Background
With the rapid development of industry, the demand for oil is increasing, a large amount of oily sewage is generated worldwide each year, but a large amount of oil enters a water body due to imperfect treatment technology, insufficient management and other reasons, and great threat is caused to the environment and human health. Compared with the traditional oily wastewater treatment technology, the ultrafiltration membrane treatment technology has the advantages of no need of adding other reagents, easy recovery or treatment of concentrated products, excellent separation performance, low equipment cost and operation cost and the like, and has a great practical application prospect. However, common organic ultrafiltration membrane materials have the defects of low water flux and easy pollution, and the practical application of the ultrafiltration membrane in the oily wastewater treatment industry is limited by the unavoidable conditions.
Disclosure of Invention
The invention provides a method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane in situ based on a metal polyphenol network, which aims to solve the technical problems of low entrapment rate of the existing ultrafiltration membrane on emulsified oil and small rejection effect of the membrane surface on emulsified oil pollutants.
The method for modifying the manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network in situ comprises the following steps:
preparing a tannic acid solution and a manganese acetate solution, uniformly stirring and mixing, adding a sodium hydroxide solution to adjust the pH value to obtain a metal polyphenol network modified solution, and infiltrating one side of an active layer of a polyethersulfone ultrafiltration membrane to be modified with the metal polyphenol network modified solution, wherein vibration is carried out in the infiltration process to obtain the metal polyphenol network modified membrane;
preparing a manganese acetate growth solution, soaking the metal polyphenol network modified film obtained in the first step in the manganese acetate growth solution, and then performing a hydrothermal reaction to obtain an amorphous manganese dioxide modified film with the surface grown;
preparing potassium permanganate solution, soaking the amorphous manganese dioxide modified film growing on the surface obtained in the step two in the potassium permanganate solution, and carrying out vibration contact reaction to obtain the delta-manganese dioxide modified film growing on the surface, thereby finishing modification.
The two sides of the polyethersulfone ultrafiltration membrane to be modified are of asymmetric structures, the front surface of the membrane is of a compact structure from the view of the cross section structure of the membrane, the bottom of the membrane downwards is of a loose finger-shaped hole structure, and one side of the active layer is a compact structure part and mainly plays a role in interception. In the filtration process, the front surface of the membrane is contacted with pollutants, and the accumulation of the pollutants on the front surface of the membrane causes membrane pollution. The purpose of membrane modification is to generate a hydrophilic modification layer on the front surface of the membrane, so that membrane pollution is effectively slowed down.
Further limited, the metal polyphenol network modified film in the first step, the amorphous manganese dioxide modified film grown on the surface in the second step and the delta-manganese dioxide modified film grown on the surface in the third step are stored in pure water for standby at the temperature of 4 ℃.
The beneficial effects of the invention are as follows:
1) The invention uses the biomineralization idea to realize the in-situ growth of metal oxide on the surface of the membrane by utilizing the metal polyphenol network modified layer, wherein the tannic acid-manganese ion metal polyphenol network modified layer is tightly combined with the surface of the membrane by means of the adhesion of tannic acid on one hand, and realizes the in-situ deposition of metal ions on the surface of the membrane by means of the complexing ability of tannic acid and metal ions on the other hand, thereby providing stable growth sites for the subsequent growth of the metal oxide and greatly improving the long-term operation stability of the modified membrane.
2) The invention realizes the in-situ growth of delta-manganese dioxide on the surface of the membrane, the material has a typical two-dimensional lamellar structure, can generate a three-dimensional nano flower micron structure through regulation and control, has the potential of reducing water resistance and improving the surface roughness of the membrane, and the delta-manganese dioxide has a certain ozone catalytic oxidation capability.
3) The method of the invention maintains higher level permeability, improves interception performance to a certain extent, greatly improves oil pollution resistance of the ultrafiltration membrane, slows down pollution degree of the membrane in the operation process, reduces cleaning frequency, reduces energy consumption and prolongs service life.
4) The invention realizes the in-situ growth of delta-manganese dioxide on the surface of the membrane, has mild reaction conditions, more controllable growth degree of manganese dioxide, is easy to operate, and has excellent large-scale production application prospect.
5) According to the invention, the metal polyphenol network modified layer is innovatively utilized, manganese dioxide is grown in situ, the surface micro-morphology of the ultrafiltration membrane is optimized, the pore size of the membrane pores is reduced, the hydrophilicity is improved, and the interception performance and the pollution resistance of the ultrafiltration membrane are improved.
6) The invention can obviously improve the removal rate of the ultrafiltration membrane to different emulsified oils, and has wide application prospect in the field of oily wastewater treatment.
The method is applied to the field of oily wastewater treatment.
Drawings
FIG. 1 shows PES, TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 Scanning electron microscope photograph and atomic force microscope photograph of @ TA-PES;
FIG. 2 shows a delta-MnO film having a delta-manganese dioxide modified film grown on the surface obtained in example I 2 X-ray diffraction pattern of @ TA-PES;
FIG. 3 shows a comparative experiment of PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 Pure water contact angle of @ TA-PES;
FIG. 4 shows a delta-MnO film having a delta-manganese dioxide modified film grown on the surface prepared in example I 2 Underwater oil drop contact angles of different oils of @ TA-PES;
FIG. 5 shows a comparative experiment of PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 Pore size distribution map of @ TA-PES;
FIG. 6 shows a comparative experiment of PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 Pure water flux histogram of @ TA-PES;
FIG. 7 shows a comparative experiment of PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 Bar graph of retention of petroleum ether, n-hexadecane, cyclohexane, soybean oil, 1, 2-dichloroethane and n-hexane emulsified oil solutions, respectively;
FIG. 8 shows a comparative experiment of PES ultrafiltration membrane and delta-MnO film with delta-manganese dioxide modified film grown on the surface obtained in example one 2 Three period contamination curve for @ TA-PES.
Detailed Description
The first embodiment is as follows: the method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network in situ is characterized by comprising the following steps of:
preparing a tannic acid solution and a manganese acetate solution, uniformly stirring and mixing, adding a sodium hydroxide solution to adjust the pH value to obtain a metal polyphenol network modified solution, and infiltrating one side of an active layer of a polyethersulfone ultrafiltration membrane to be modified with the metal polyphenol network modified solution, wherein vibration is carried out in the infiltration process to obtain the metal polyphenol network modified membrane;
preparing a manganese acetate growth solution, soaking the metal polyphenol network modified film obtained in the first step in the manganese acetate growth solution, and then performing a hydrothermal reaction to obtain an amorphous manganese dioxide modified film with the surface grown;
preparing potassium permanganate solution, soaking the amorphous manganese dioxide modified film growing on the surface obtained in the step two in the potassium permanganate solution, and carrying out vibration contact reaction to obtain the delta-manganese dioxide modified film growing on the surface, thereby finishing modification.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the metal polyphenol network modifying solution in the first step is completed according to the following steps:
step 1, dissolving 0.06-0.18 g of tannic acid in 30-90 mL of pure water, dissolving 0.06-0.18 g of manganese acetate in 30-90 mL of pure water, and carrying out ultrasonic dissolution in an air environment to obtain a tannic acid solution and a manganese acetate solution;
and 2, mixing the tannic acid solution obtained in the step 1 with the manganese acetate solution, regulating the pH value by adopting a sodium hydroxide solution, controlling the rotating speed to be 200-300 r/min, and uniformly mixing to obtain the metal polyphenol network modified solution. The other steps are the same as those of the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: in the first step, the tannic acid solution and the manganese acetate solution are mixed in a volume ratio of 1:1. Others are the same as those of the embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the concentration of the sodium hydroxide solution in the first step is 0.01mol/L to 0.05mol/L. The other embodiments are the same as one to three.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and step one, regulating the pH value to be 5.5-6.5. Others are identical to one fourth of the embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: controlling the oscillation speed to be 40-80 rmp/min, and the oscillation time to be 2-6 h. The others are the same as those of the embodiment examples one to five.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: and step two, preparing a manganese acetate growth solution with the concentration of 0.1-0.3 wt% and pure water as a solvent. The others are the same as those of the embodiment examples one to six.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and step two, carrying out hydrothermal reaction, wherein the reaction temperature is controlled to be 50-70 ℃ and the reaction time is controlled to be 1-3 h. The others are the same as those of the embodiment examples one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: and thirdly, preparing the potassium permanganate solution with the concentration of 0.005-0.01 wt% and pure water as the solvent. The others are the same as one to eight of the embodiments.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: and step three, controlling the oscillation speed to be 40-80 r/min, and the oscillation time to be 2-180 min. The others are the same as those of one of the embodiments.
The present invention is not limited to the above embodiments, and the object of the invention can be achieved by one or a combination of several embodiments.
Embodiment one:
the method for modifying manganese dioxide grown on the surface of the ultrafiltration membrane based on the metal polyphenol network in situ comprises the following steps:
preparing a tannic acid solution with the concentration of 2g/L and a manganese acetate solution with the concentration of 2g/L, stirring and mixing uniformly, adding a sodium hydroxide solution with the concentration of 0.025mol/L to adjust the pH value to 5.8 to obtain a metal polyphenol network modified solution, fixing a polyether sulfone ultrafiltration membrane (PES) to be modified on a reactor, and infiltrating one side of an active layer of the polyether sulfone ultrafiltration membrane to be modified by using the metal polyphenol network modified solution, wherein vibration is carried out in the infiltration process, the vibration speed is controlled to be 60rmp/min, and the vibration time is 4 hours to obtain the metal polyphenol network modified membrane (TA/Mn-PES);
preparing a manganese acetate growth solution with the concentration of 0.2wt%, immersing the metal polyphenol network modified film obtained in the first step in the manganese acetate growth solution, and then performing a hydrothermal reaction, wherein the reaction temperature is controlled to be 60 ℃, and the reaction time is controlled to be 2 hours, so as to obtain an amorphous manganese dioxide modified film with the surface growing;
preparing a potassium permanganate solution with the concentration of 0.005wt%, immersing the amorphous manganese dioxide modified film with the surface grown in the potassium permanganate solution, carrying out oscillation contact reaction, controlling the oscillation speed to be 60r/min, and carrying out oscillation for 20min to obtain the modified film with the surface grown delta-manganese dioxide (delta-MnO) 2 @ TA-PES), the modification was completed.
The metal polyphenol network modifying solution in the first step is completed according to the following steps:
step 1, dissolving 0.12g of tannic acid in 60mL of pure water, dissolving 0.12g of manganese acetate in 60mL of pure water, and performing ultrasonic dissolution in an air environment to obtain a tannic acid solution and a manganese acetate solution;
and 2, mixing the tannic acid solution obtained in the step 1 with a manganese acetate solution, regulating the pH value to 5.8 by adopting a sodium hydroxide solution with the concentration of 0.025mol/L, and uniformly mixing at the rotating speed of 250r/min to obtain the metal polyphenol network modified solution.
Comparison experiment: the difference between this comparative experiment and example one is: the PES is not subjected to surface modification and in-situ mineralization of a metal polyphenol network, and is soaked in isopropanol to remove a protective agent, and then soaked in pure water to obtain the PES ultrafiltration membrane.
Detection test
FIG. 1 shows PES, TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 Scanning electron microscope photograph and atomic force microscope photograph of @ TA-PES; wherein figure a 1 Surface topography at 2 ten thousand magnification for PES, panel a 2 Surface topography at 10 ten thousand magnification for PES, panel a 3 Atomic force microscopy of PES, panel b 1 Surface topography at 2 ten thousand magnification for TA/Mn-PES, panel b 2 Surface topography at 10 ten thousand magnification for TA/Mn-PES, panel b 3 Atomic force microscope image for TA/Mn-PES, panel c 1 Surface morphology at 2 ten thousand times magnification for MnO@TA-PES, panel c 2 Surface topography at 10 ten thousand times magnification for MnO@TA-PES, panel c 3 Atomic force microscope image of MnO@TA-PES, panel d 1 Is delta-MnO 2 Surface morphology of @ TA-PES at 2-thousand times magnification, panel d 2 Is delta-MnO 2 Surface morphology of @ TA-PES at 10-thousand magnification, panel d 3 Is delta-MnO 2 Atomic force microscopy of @ TA-PES.
(II) FIG. 2 shows a delta-MnO film having a delta-manganese dioxide modified film grown on the surface obtained in example one 2 X-ray diffraction pattern of @ TA-PES, as can be seen from FIG. 2, delta-MnO 2 Diffraction peaks at 13.0 °, 24.2 °, 36.7 ° and 65.9 ° appear for @ TA, with delta-MnO 2 The appearance positions of characteristic peaks are very close to each other, which proves that delta-MnO grows on the surface of the film in situ 2 The feasibility of the method for realizing the in-situ growth of the metal oxide on the surface of the film by utilizing the metal polyphenol network is verified.
(III) FIG. 3 shows a comparative experiment PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 As can be seen from FIG. 3, the pure water contact angle of the comparative film PES was 70.7℃and the pure water contact angle of the metal polyphenol network modified film TA/Mn-PES was 22.3℃and the pure water contact angle of the amorphous manganese dioxide modified film MnO@TA-PES grown on the surface was 11.5℃and the delta-manganese dioxide modified film delta-MnO grown on the surface 2 The pure water contact angle of @ TA-PES was close to 0℃and was compared with the control film, delta-MnO 2 The pure water contact angle of the @ TA-PES film is obviously reduced, and the hydrophilicity is obviously improved.
(IV) FIG. 4 shows a delta-MnO film with a delta-manganese dioxide modified film grown on the surface prepared in example one 2 Different oil-in-water drop contact angles of TA-PES, it can be seen from FIG. 4 that the surface was grown with delta-manganese dioxide modified film delta-MnO 2 Petroleum ether contact angle of @ TA-PES is 165.6 degrees, and delta-manganese dioxide modified film delta-MnO is grown on the surface 2 The n-hexadecane contact angle of the @ TA-PES is 168.6 degrees, and a delta-manganese dioxide modified film delta-MnO is grown on the surface 2 Cyclohexane contact angle of @ TA-PES is 165.2 DEG, and delta-manganese dioxide modified film delta-MnO is grown on the surface 2 Soybean oil contact angle of @ TA-PES is 166.7 DEG, and delta-manganese dioxide modified film delta-MnO is grown on the surface 2 1, 2-dichloroethane contact angle of @ TA-PES is 150.1 DEG, and delta-manganese dioxide modified film delta-MnO is grown on the surface 2 N-hexane contact angle of @ TA-PES was 163.9 °, delta-MnO 2 The contact angle of underwater oil drops of the @ TA-PES film is larger than 150 degrees,exhibits excellent repelling effect on oil droplets.
(fifth) FIG. 5 shows a comparative experiment PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 Pore size distribution plot of @ TA-PES, wherein plot a is PES, plot b is TA/Mn-PES, plot c is MnO @ TA-PES, and plot d is delta-MnO 2 @TA-PES; from fig. 5, it can be seen that the metal polyphenol network modified solution is deposited on the ultrafiltration membrane surface but does not cause reduction of membrane pores, and after manganese dioxide grows on the subsequent membrane surface in situ, the manganese dioxide nanosheets partially cover the membrane pores, so that the membrane pore size is slightly reduced, and the membrane pore size is further regulated and controlled along with the improvement of the crystallinity of the manganese dioxide, so that the membrane pore size is reduced and more uniform.
FIG. 6 shows a comparative experiment of PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 As can be seen from FIG. 6, the pure water flux histogram of the @ TA-PES film was 293.9L.m -2 ·h -1 The pure water flux of the metal polyphenol network modified membrane TA/Mn-PES is 601.9 L.m -2 ·h -1 The pure water flux of the amorphous manganese dioxide modified membrane MnO@TA-PES grown on the surface is 523.8 L.m -2 ·h -1 delta-MnO with delta-manganese dioxide modified film grown on the surface 2 The pure water flux of @ TA-PES was 389.4 L.m -2 ·h -1 The ultrafiltration membrane after modification has a reduced pore size and an increased water resistance compared to the control membrane, but maintains a higher level of permeability due to a significant increase in hydrophilicity.
FIG. 7 shows a comparative experiment of PES ultrafiltration membrane and TA/Mn-PES, mnO@TA-PES and delta-MnO in example one 2 The retention bar graph of TA-PES on petroleum ether, n-hexadecane, cyclohexane, soybean oil, 1, 2-dichloroethane and n-hexane emulsified oil solutions (concentration of 10g/L, concentration of 1g/L of surfactant SDS) respectively; wherein 1 represents PES,2 represents TA/Mn-PES,3 represents MnO@TA-PES, and 4 represents delta-MnO 2 @ TA-PES. As can be seen from FIG. 7, the petroleum ether emulsified oil retention rate of the control film PES was 98.3%, the n-hexadecane emulsified oil retention rate of the control film PES was 99.7%, the cyclohexane emulsified oil retention rate of the control film PES was 88.1%, and the soybean oil emulsified oil retention rate of the control film PES was 98.4 percent, the retention rate of the 1, 2-dichloroethane emulsified oil of the control film PES is 95.6 percent, and the retention rate of the n-hexane emulsified oil of the control film PES is 92.0 percent; the retention rate of petroleum ether emulsified oil of the metal polyphenol network modified membrane TA/Mn-PES is 98.7%, the retention rate of n-hexadecane emulsified oil of the metal polyphenol network modified membrane TA/Mn-PES is 99.7%, the retention rate of cyclohexane emulsified oil of the metal polyphenol network modified membrane TA/Mn-PES is 92.9%, the retention rate of soybean oil emulsified oil of the metal polyphenol network modified membrane TA/Mn-PES is 98.4%, the retention rate of 1, 2-dichloroethane emulsified oil of the metal polyphenol network modified membrane TA/Mn-PES is 98.3%, and the retention rate of n-hexane emulsified oil of the metal polyphenol network modified membrane TA/Mn-PES is 94.4%; the retention rate of petroleum ether emulsified oil of which the surface is provided with an amorphous manganese dioxide modified membrane MnO@TA-PES is 98.7%, the retention rate of n-hexadecane emulsified oil of which the surface is provided with an amorphous manganese dioxide modified membrane MnO@TA-PES is 99.8%, the retention rate of cyclohexane emulsified oil of which the surface is provided with an amorphous manganese dioxide modified membrane MnO@TA-PES is 94.2%, the retention rate of soybean oil emulsified oil of which the surface is provided with an amorphous manganese dioxide modified membrane MnO@TA-PES is 99.2%, the retention rate of 1, 2-dichloroethane emulsified oil of which the surface is provided with an amorphous manganese dioxide modified membrane MnO@TA-PES is 96.2%, and the retention rate of n-hexane emulsified oil of which the surface is provided with an amorphous manganese dioxide modified membrane MnO@TA-PES is 94.8%; delta-MnO with delta-manganese dioxide modified film grown on surface 2 Petroleum ether emulsified oil retention rate of @ TA-PES is 99.0%, and delta-manganese dioxide modified membrane delta-MnO grows on the surface 2 The retention rate of n-hexadecane emulsified oil of the @ TA-PES is 99.7%, and a delta-manganese dioxide modified membrane delta-MnO grows on the surface of the n-hexadecane emulsified oil 2 Cyclohexane emulsified oil retention rate of 98.6 percent, and delta-manganese dioxide modified membrane delta-MnO growing on the surface 2 Soybean oil emulsified oil retention rate of @ TA-PES is 99.3%, and delta-manganese dioxide modified membrane delta-MnO is grown on the surface 2 The retention rate of the 1, 2-dichloroethane emulsified oil of the @ TA-PES is 98.4 percent, and a delta-manganese dioxide modified membrane delta-MnO grows on the surface of the emulsified oil 2 The retention rate of the n-hexane emulsion oil of the @ TA-PES is 98.2%. Compared with a control film, the interception performance of the ultrafiltration film after modification is improved to a certain extent.
FIG. 8 shows the surface growth of the PES ultrafiltration membrane and the sample obtained in example onedelta-MnO with delta-manganese dioxide modified film 2 Three cycle pollution curve of TA-PES (n-hexadecane emulsified oil, n-hexadecane concentration 10g/L, surfactant SDS concentration 1 g/L), wherein ■ represents PES, +. 2 @ TA-PES. As can be seen from FIG. 8, the surface was grown with a delta-manganese dioxide modified film delta-MnO as compared with the control film 2 The pollution degree of the @ TA-PES is obviously reduced, and the oil pollution resistance is obviously improved.
Claims (10)
1. The method for modifying the manganese dioxide grown on the surface of the ultrafiltration membrane based on the metal polyphenol network in situ is characterized by comprising the following steps of:
preparing a tannic acid solution and a manganese acetate solution, uniformly stirring and mixing, adding a sodium hydroxide solution to adjust the pH value to obtain a metal polyphenol network modified solution, and infiltrating one side of an active layer of a polyethersulfone ultrafiltration membrane to be modified with the metal polyphenol network modified solution, wherein vibration is carried out in the infiltration process to obtain the metal polyphenol network modified membrane;
preparing a manganese acetate growth solution, soaking the metal polyphenol network modified film obtained in the first step in the manganese acetate growth solution, and then performing a hydrothermal reaction to obtain an amorphous manganese dioxide modified film with the surface grown;
preparing potassium permanganate solution, soaking the amorphous manganese dioxide modified film growing on the surface obtained in the step two in the potassium permanganate solution, and carrying out vibration contact reaction to obtain the delta-manganese dioxide modified film growing on the surface, thereby finishing modification.
2. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network according to claim 1, wherein the metal polyphenol network modifying solution in the step one is prepared by the following steps:
step 1, dissolving 0.06-0.18 g of tannic acid in 30-90 mL of pure water, dissolving 0.06-0.18 g of manganese acetate in 30-90 mL of pure water, and carrying out ultrasonic dissolution in an air environment to obtain a tannic acid solution and a manganese acetate solution;
and 2, mixing the tannic acid solution obtained in the step 1 with the manganese acetate solution, regulating the pH value by adopting a sodium hydroxide solution, controlling the rotating speed to be 200-300 r/min, and uniformly mixing to obtain the metal polyphenol network modified solution.
3. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network according to claim 1, wherein in the step one, the tannic acid solution and the manganese acetate solution are mixed in a volume ratio of 1:1.
4. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network according to claim 1, wherein the concentration of the sodium hydroxide solution in the step one is 0.01mol/L to 0.05mol/L.
5. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network according to claim 1, wherein the pH value is adjusted to 5.5-6.5 in the first step.
6. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network according to claim 1, wherein the vibration speed is controlled to be 40-80 rmp/min, and the vibration time is controlled to be 2-6 h.
7. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network in situ according to claim 1, wherein the concentration of manganese acetate growth solution prepared in the second step is 0.1-0.3 wt%, and the solvent is pure water.
8. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network in situ according to claim 1, wherein the hydrothermal reaction in the second step is controlled at 50-70 ℃ for 1-3 h.
9. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network in situ according to claim 1, wherein the concentration of the potassium permanganate solution prepared in the step three is 0.005-0.01 wt%, and the solvent is pure water.
10. The method for modifying manganese dioxide grown on the surface of an ultrafiltration membrane based on a metal polyphenol network in situ according to claim 1, wherein the vibration speed is controlled to be 40-80 r/min in the third step, and the vibration time is controlled to be 2-180 min.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE877806A (en) * | 1978-07-20 | 1979-11-16 | Nippon Steel Corp | MANGANESE COATING DEPOSITED ON STEEL MATERIALS |
| JPS5518513A (en) * | 1978-07-20 | 1980-02-08 | Nippon Steel Corp | Electroplating apparatus with manganese |
| JP2011038173A (en) * | 2009-08-17 | 2011-02-24 | Nippon Parkerizing Co Ltd | Post-treatment liquid for self-deposition coating film on metal surface, and method for producing metal material having post-treated self-deposition coating film formed thereon |
| CN107266039A (en) * | 2017-06-06 | 2017-10-20 | 苏州轩朗塑料制品有限公司 | A kind of preparation method and applications of medical environment-friendly composite material |
| CN110280227A (en) * | 2019-07-04 | 2019-09-27 | 青岛科技大学 | MnO2The preparation and its application of the difunctional composite material of/PEI/TA |
| CN112717706A (en) * | 2020-11-03 | 2021-04-30 | 浙江师范大学 | Metal organic framework ZIF-8 film, preparation method and application thereof |
| CN113690429A (en) * | 2021-08-23 | 2021-11-23 | 武汉立承科技有限公司 | Carbon-coated graphene/metal oxide composite material and preparation method thereof |
| CN114084907A (en) * | 2021-10-26 | 2022-02-25 | 西安交通大学 | Mesoporous manganese dioxide synthesized by redox method, metal-doped mesoporous manganese dioxide and method |
| TW202211530A (en) * | 2020-05-07 | 2022-03-16 | 美商福恩能源公司 | Rechargeable battery using iron negative electrode and manganese oxide positive electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110044981A (en) * | 2008-06-25 | 2011-05-03 | 나노바이오매터스, 에스. 엘. | Active Nanocomposite Materials and Methods for Making the Same |
-
2022
- 2022-09-08 CN CN202211097275.2A patent/CN115463564B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE877806A (en) * | 1978-07-20 | 1979-11-16 | Nippon Steel Corp | MANGANESE COATING DEPOSITED ON STEEL MATERIALS |
| JPS5518513A (en) * | 1978-07-20 | 1980-02-08 | Nippon Steel Corp | Electroplating apparatus with manganese |
| JP2011038173A (en) * | 2009-08-17 | 2011-02-24 | Nippon Parkerizing Co Ltd | Post-treatment liquid for self-deposition coating film on metal surface, and method for producing metal material having post-treated self-deposition coating film formed thereon |
| CN107266039A (en) * | 2017-06-06 | 2017-10-20 | 苏州轩朗塑料制品有限公司 | A kind of preparation method and applications of medical environment-friendly composite material |
| CN110280227A (en) * | 2019-07-04 | 2019-09-27 | 青岛科技大学 | MnO2The preparation and its application of the difunctional composite material of/PEI/TA |
| TW202211530A (en) * | 2020-05-07 | 2022-03-16 | 美商福恩能源公司 | Rechargeable battery using iron negative electrode and manganese oxide positive electrode |
| CN112717706A (en) * | 2020-11-03 | 2021-04-30 | 浙江师范大学 | Metal organic framework ZIF-8 film, preparation method and application thereof |
| CN113690429A (en) * | 2021-08-23 | 2021-11-23 | 武汉立承科技有限公司 | Carbon-coated graphene/metal oxide composite material and preparation method thereof |
| CN114084907A (en) * | 2021-10-26 | 2022-02-25 | 西安交通大学 | Mesoporous manganese dioxide synthesized by redox method, metal-doped mesoporous manganese dioxide and method |
Non-Patent Citations (1)
| Title |
|---|
| 多酚-金属络合物改性膜的制备及除锰性能研究;闫佳莹;中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(第2022年第03期);B016-175 * |
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