CN115463559A - Method for enhanced cleaning of polluted delta-manganese dioxide modified membrane based on peroxymonosulfate catalytic oxidation - Google Patents
Method for enhanced cleaning of polluted delta-manganese dioxide modified membrane based on peroxymonosulfate catalytic oxidation Download PDFInfo
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- 238000004140 cleaning Methods 0.000 title claims abstract description 55
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
-
- 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
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- Chemical & Material Sciences (AREA)
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- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A method for intensively cleaning a polluted delta-manganese dioxide modified membrane based on catalytic oxidation of peroxymonosulfate belongs to the field of modification of membrane cleaning methods. The method aims to solve the problem that the existing delta-manganese dioxide modified membrane seriously pollutes the membrane in the long-term filtration process of emulsified oil. The method comprises the following steps: soaking the polluted delta-manganese dioxide modified membrane in a peroxymonosulfate aqueous solution, and standing for contact reaction. According to the method, the permonosulfate is selected as a catalytic cleaning reagent, the permonosulfate has the advantages of easiness in storage, long shelf life, safety in operation, strong activity, low price and the like, in-situ catalytic oxidation of the permonosulfate is realized, active substances are generated on the surface of the membrane, oil drops adhered to the surface of the membrane are degraded, pollutants on the surface of the membrane are effectively removed, the performance of the membrane is recovered to the original level after cleaning, irreversible pollution is remarkably reduced, and the pollution degree of the organic ultrafiltration membrane in the emulsified oil treatment process is remarkably inhibited. The invention is suitable for the reinforced cleaning of the polluted delta-manganese dioxide modified membrane.
Description
Technical Field
The invention belongs to the field of modification of membrane cleaning methods, and particularly relates to a method for intensively cleaning a polluted delta-manganese dioxide modified membrane based on catalytic oxidation of peroxymonosulfate.
Background
The demand for petroleum is rapidly increasing due to the acceleration of the industrialization process, and the effective treatment of the oily wastewater is more and more called. The ultrafiltration membrane is used as a green and efficient water treatment technology, can effectively treat emulsified oil wastewater, and has a great practical application prospect. However, due to the hydrophobic effect between the membrane surface and the oil drops, the oil drops are easy to adhere to the membrane surface or block the membrane pores, membrane pollution is inevitable, and the performance of the ultrafiltration membrane is usually reduced remarkably in the long-term operation process. Common membrane cleaning methods include physical cleaning, which can remove some reversible contamination, and chemical cleaning, which is not efficient for irreversible contamination. The chemical cleaning can effectively remove irreversible pollution and realize better flux recovery rate. However, in the chemical cleaning process, the polluted membrane is often required to be soaked in a high-concentration acid-alkali solution for a long time, and in the long-term operation process, the conventional chemical cleaning can damage the membrane to a certain extent, reduce the filtration performance of the membrane, shorten the service life of the membrane, and limit the practical application of the ultrafiltration membrane in the oily wastewater treatment industry.
Based on the size screening effect, the membrane separation technology has a good interception effect on the oily wastewater. However, as the filtration time increases, the trapped oil droplets continue to build up on the membrane surface, causing severe membrane fouling. Under the attraction of the hydrophobic effect of the oil drops/the organic membrane, the oil drops adhere to the surface of the membrane to block the membrane pores, and the continuous oil membrane is gradually formed on the surface of the membrane due to the expansion effect of the oil drops, so that the performance of the membrane is rapidly reduced.
Disclosure of Invention
The invention aims to solve the problem of serious membrane pollution of the existing delta-manganese dioxide modified membrane in the long-term filtration process of emulsified oil, and provides a method for intensively cleaning the polluted delta-manganese dioxide modified membrane based on peroxymonosulfate catalytic oxidation.
A method for strengthening and cleaning a polluted delta-manganese dioxide modified membrane based on peroxymonosulfate catalytic oxidation is characterized in that the polluted delta-manganese dioxide modified membrane is soaked in a peroxymonosulfate aqueous solution, and after standing contact reaction, the strengthening and cleaning of the delta-manganese dioxide modified membrane is completed;
the polluted delta-manganese dioxide modified membrane is a delta-manganese dioxide modified membrane after oily wastewater is treated;
the concentration of the aqueous solution of the peroxymonosulfate is 0.1 to 0.3mM;
the standing contact reaction: the temperature is 20-30 ℃, the reaction time is 2-7min, and the pH is 7.
The invention aims at intensively cleaning a polluted delta-manganese dioxide modified membrane, which utilizes a metal polyphenol network modified layer to realize in-situ growth of metal oxides on the surface of the membrane, wherein the tannin-manganese ion metal polyphenol network modified layer is tightly combined with the surface of the membrane by the self adhesive force of tannin on the one hand, and the metal ions are deposited on the surface of the membrane in situ by the complexing ability of the tannin and the metal ions on the other hand, so that stable growth sites are provided for the subsequent growth of the metal oxides, the layered delta-manganese dioxide has abundant catalytic active sites, and the substance is used as a modified substance on the surface of the ultrafiltration membrane, so that the catalytic activity of the ultrafiltration membrane can be greatly improved, and compared with the method of filtering commercial manganese dioxide to the surface of the membrane to obtain the manganese dioxide modified membrane, the modified membrane obtained by in-situ growth has better stability.
The method solves the problems that irreversible pollution cannot be effectively removed and the performance of the membrane cannot be recovered to the original level by cleaning the polluted ultrafiltration membrane by a conventional physical and chemical cleaning method. Because the active substance has extremely short time, compared with the conventional catalytic cleaning by adding a catalyst/oxidant, the method realizes the in-situ generation of the active substance on the surface of the membrane, removes the pollutants on the surface of the membrane and in part of membrane pores in a targeted manner, and has higher utilization rate of the active substance and better cleaning effect; meanwhile, the required cleaning time is shorter, and the required consumed oxidant dosage is smaller.
According to the method, the peroxymonosulfate is selected as the catalytic cleaning reagent, the peroxymonosulfate has the advantages of easiness in storage, long shelf life, safety in operation, strong activity, low price and the like, in-situ peroxymonosulfate catalytic oxidation is realized, active substances are generated on the surface of the membrane, oil drops adhered to the surface of the membrane are degraded, effective removal of pollutants on the surface of the membrane is realized, the performance of the polluted modified ultrafiltration membrane is restored to the original level after catalytic cleaning of the peroxymonosulfate, irreversible pollution is remarkably reduced, the pollution degree of the organic ultrafiltration membrane in the emulsified oil treatment process is remarkably inhibited by the enhanced cleaning mode, the practical application of the organic ultrafiltration membrane in the field of oil-water separation is expected to be widened, and the advantages are displayed.
The invention is suitable for the reinforced cleaning of the polluted delta-manganese dioxide modified membrane.
Drawings
FIG. 1 is SEM scanning electron microscope image of in-situ grown manganese dioxide modified ultrafiltration membrane in the example;
FIG. 2 is a TEM transmission microscopic image of the in-situ grown manganese dioxide modified ultrafiltration membrane in the example;
FIG. 3 is a specific flux curve diagram of the in-situ grown manganese dioxide modified ultrafiltration membrane in the example, wherein, \9633indicateshydraulic cleaning, and O indicates PMS catalytic cleaning;
FIG. 4 is a diagram showing peaks characteristic to the detection of radicals in the example, in which
Denotes DMPO-. OH, \\ 9679, denotes DMPO-SO 4 ·- ；
FIG. 5 is a graph of characteristic peaks of non-radical detection in the example, wherein diamond-solid represents TEMP- 1 O 2 ；
FIG. 6 is a bar graph of flux recovery rates of in-situ grown manganese dioxide modified ultrafiltration membranes after contamination in different cleaning modes in the examples;
fig. 7 is a bar graph of the degree of contamination of the in situ grown manganese dioxide modified ultrafiltration membrane of the example after different cleaning modes, wherein a represents the reversible contamination ratio and b represents the irreversible contamination ratio.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first specific implementation way is as follows: the embodiment of the invention relates to a method for intensively cleaning a polluted delta-manganese dioxide modified membrane based on catalytic oxidation of peroxymonosulfate, which comprises the steps of soaking the polluted delta-manganese dioxide modified membrane in a peroxymonosulfate aqueous solution, standing for contact reaction, and then finishing the intensive cleaning of the delta-manganese dioxide modified membrane.
The second embodiment is as follows: the difference between the embodiment and the first embodiment is that the polluted delta-manganese dioxide modified membrane is a delta-manganese dioxide modified membrane after oily wastewater is treated. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first embodiment in that the concentration of the aqueous solution of monopersulfate is 0.1 to 0.3mM. The rest is the same as the first embodiment.
The fourth concrete implementation mode: this embodiment is different from the third embodiment in that the concentration of the aqueous solution of monopersulfate is 0.2mM. The rest is the same as the third embodiment.
The fifth concrete implementation mode is as follows: the difference between the embodiment and the first embodiment is that the standing contact reaction: the temperature is 20-30 ℃, the reaction time is 2-7min, and the pH is 7. The rest is the same as the first embodiment.
The sixth specific implementation mode: the present embodiment is different from the fifth embodiment in that the standing contact reaction: the temperature was 25 ℃, the reaction time was 5min, and the pH was 7. The rest is the same as the fifth embodiment.
The beneficial effects of the present invention are demonstrated by the following examples:
example (b):
a method for strengthening and cleaning a polluted delta-manganese dioxide modified membrane based on catalytic oxidation of peroxymonosulfate comprises the steps of soaking the polluted delta-manganese dioxide modified membrane in a peroxymonosulfate aqueous solution, standing for contact reaction, and then completing the strengthening and cleaning of the delta-manganese dioxide modified membrane.
In this example, the contaminated δ -manganese dioxide modified membrane is a δ -manganese dioxide modified membrane after treatment of oily wastewater.
The concentration of the aqueous solution of Peroxymonosulfate (PMS) described in this example was 0.2mM.
The standing contact reaction described in this example: the temperature was 25 ℃, the reaction time was 5min, and the pH was 7.
The preparation method of the delta-manganese dioxide modified membrane in the embodiment is as follows:
preparing a tannic acid solution and a manganese acetate solution, stirring and mixing uniformly, adding a sodium hydroxide solution to adjust the pH value to obtain a metal polyphenol network modified solution, infiltrating one side of an active layer of a polyether sulfone ultrafiltration membrane to be modified with the metal polyphenol network modified solution, and obtaining a metal polyphenol network modified membrane (TA/Mn-PES) by oscillating in the infiltration process;
step two, preparing a manganese acetate growth solution, soaking the metal polyphenol network modified film obtained in the step one in the manganese acetate growth solution, and then carrying out hydrothermal reaction to obtain a modified film (MnO) with amorphous manganese dioxide growing on the surface x @TA-PES)；
Step three, preparing a 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 performing oscillation contact reaction to obtain a delta-manganese dioxide modified film (delta-MnO) growing on the surface 2 @ TA-PES), modification is completed;
the metal polyphenol network modification solution in the first step is completed according to the following steps:
step 2, mixing the tannic acid solution obtained in the step 1 with a manganese acetate solution, then adjusting the pH value by adopting a sodium hydroxide solution, controlling the rotating speed to be 200r/min, and uniformly mixing to obtain a metal polyphenol network modified solution;
the volume ratio of the tannic acid solution to the manganese acetate solution in the step 2 is 1;
the concentration of the sodium hydroxide solution in the first step is 0.03mol/L;
regulating the pH value to 6;
step one, controlling the oscillation speed to be 60rmp/min and the oscillation time to be 4h;
step two, preparing a manganese acetate growth solution with the concentration of 0.2wt% and pure water as a solvent;
secondly, performing hydrothermal reaction, wherein the reaction temperature is controlled to be 60 ℃, and the reaction time is 2 hours;
step three, preparing a potassium permanganate solution with the concentration of 0.005wt% and a solvent of pure water;
and step three, controlling the oscillation speed to be 60r/min and the oscillation time to be 20min.
In the embodiment, the delta-manganese dioxide modified membrane is subjected to an n-hexadecane emulsified oil separation experiment to obtain a polluted delta-manganese dioxide modified membrane;
in the separation experiment of the n-hexadecane emulsified oil, the oil concentration is 10g/L; the surfactant is sodium dodecyl sulfate, and the concentration is 0.1g/L; the volume ratio of oil to water is 1; the emulsified oil was stirred by a high speed homogenizer at 12000rpm/min for 15min.
Comparative example: the comparative experiment differs from the examples in that: the ultrafiltration membrane (PES) is not subjected to surface modification and in-situ mineralization of a metal polyphenol network, only isopropanol is used for soaking to remove a protective agent, and then the cleaned commercial ultrafiltration membrane is soaked in pure water.
And (3) detection test:
FIG. 1 shows delta-MnO in examples 2 Scanning electron micrograph of @ TA-PES showing delta-MnO 2 @ TA-PES surface topography under 2 ten thousand times magnification, respectively.
FIG. 2 shows delta-MnO in example 2 TEM transmission microscopy of @ TA-PES, as can be seen from FIG. 2, delta-MnO 2 The lattice spacing of @ TA is 0.69nm, which is consistent with the delta-MnO reported in the literature 2 The crystal form of manganese dioxide grown in situ on the surface of the film is proved to be delta-MnO 2 The feasibility of the method that the metal oxide can be grown on the surface of the film in situ by utilizing the metal polyphenol network is verified.
(III) FIG. 3 is a view showing delta-MnO in example 2 The specific flux curve of @ TA-PES, as can be seen from FIG. 3, is the delta-MnO after contamination 2 After the @ TA-PES is subjected to hydraulic cleaning and PMS catalytic cleaning, the flux is recovered to different degrees, and compared with the hydraulic cleaning, the PMS catalytic cleaning shows higher cleaning efficiency.
(IV) FIG. 4 shows PES in comparative example and delta-MnO in example 2 The characteristic peak pattern of radical detection of @ TA-PES is shown in FIG. 4, and δ -MnO 2 @ TA-PES/PMS system detects DMPO-SO 4 Characteristic peaks of-and DMPO-OH, and the characteristic peaks increase with time, confirming delta-MnO 2 The @ TA-PES/PMS catalytic oxidation system can generate SO 4 ·- And. OH free radical, the inverse PES/PMS has no obvious characteristic peak signal.
(V) FIG. 5 shows PES in comparative example and delta-MnO in example 2 The characteristic peak pattern of non-radical detection of @ TA-PES is shown in FIG. 5, and δ -MnO 2 TEMP-plus detected by @ TA-PES/PMS system 1 O 2 Characteristic peaks, and the characteristic peaks increase with time, confirming delta-MnO 2 The catalytic oxidation system of @ TA-PES/PMS can generate non-free radicals 1 O 2 The active substance, the inverse PES/PMS, has no obvious characteristic peak signal.
(sixth) FIG. 6 shows delta-MnO in example 2 Histogram of flux recovery after @ TA-PES contamination by different cleaning modes, as can be seen from FIG. 6, delta-MnO 2 The flux recovery rate of the @ TA-PES is 81.5% after hydraulic backwashing, and the flux is recovered to 99.5% of the initial flux after PMS catalytic cleaning, and is almost recovered to a new membrane state.
(VII) FIG. 7 shows delta-MnO in example 2 The pollution degree of @ TA-PES after different cleaning modes and different cleaning modes is shown in figure 7, the reversible pollution proportion is improved to 73.7% and the irreversible pollution is only 0.5% after PMS catalysis is clear, the high-efficiency removal capacity of PMS catalysis cleaning on the irreversible pollution is proved, and in comparison with the delta-MnO after hydraulic cleaning 2 The reversible pollution proportion of @ TA-PES is 55.5%, the irreversible pollution proportion is 18.5%, and the irreversible pollution cannot be effectively removed by hydraulic cleaning.
Claims (6)
1. A method for strengthening and cleaning a polluted delta-manganese dioxide modified membrane based on catalytic oxidation of peroxymonosulfate is characterized in that the polluted delta-manganese dioxide modified membrane is soaked in a peroxymonosulfate aqueous solution, and after standing contact reaction, the strengthening and cleaning of the delta-manganese dioxide modified membrane is completed.
2. The method for intensively cleaning the polluted delta-manganese dioxide modified membrane based on the catalytic oxidation of the peroxymonosulfate as claimed in claim 1, wherein the polluted delta-manganese dioxide modified membrane is the delta-manganese dioxide modified membrane after the oily wastewater is treated.
3. The method for enhanced cleaning of contaminated delta-manganese dioxide modified membranes based on catalytic oxidation of peroxymonosulfate as claimed in claim 1, wherein the concentration of the aqueous solution of peroxymonosulfate is in the range of 0.1 to 0.3mM.
4. The method for enhanced cleaning of contaminated delta-manganese dioxide modified membranes based on catalytic oxidation of peroxymonosulfate as set forth in claim 1, wherein the aqueous solution of peroxymonosulfate is at a concentration of 0.2mM.
5. The method for enhanced cleaning of the polluted delta-manganese dioxide modified membrane based on the catalytic oxidation of the peroxymonosulfate as claimed in claim 1, wherein the standing contact reaction is as follows: the temperature is 20-30 ℃, the reaction time is 2-7min, and the pH is 7.
6. The method for enhanced cleaning of a contaminated delta-manganese dioxide modified membrane based on peroxymonosulfate catalytic oxidation as claimed in claim 1, wherein said static contact reaction: the temperature was 25 ℃, the reaction time was 5min, and the pH was 7.
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| CN202211097240.9A CN115463559A (en) | 2022-09-08 | 2022-09-08 | Method for enhanced cleaning of polluted delta-manganese dioxide modified membrane based on peroxymonosulfate catalytic oxidation |
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