CN115041021A - Molybdenum disulfide composite membrane, and preparation method, cleaning method and application thereof - Google Patents
Molybdenum disulfide composite membrane, and preparation method, cleaning method and application thereof Download PDFInfo
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- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- B01D67/0039—Inorganic membrane manufacture
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
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Abstract
The invention provides a preparation method of a molybdenum disulfide composite membrane, wherein a molybdenum disulfide dispersion liquid forms a molybdenum disulfide functional layer on the surface of a flat polyether sulfone membrane in a pressure-assisted filtration self-assembly mode. The prepared molybdenum disulfide composite membrane is cleaned by hydrogen peroxide solution. The molybdenum disulfide composite membrane prepared by the invention has excellent catalytic performance, good mechanical performance and very obvious membrane cleaning effect, and can better solve the problems of organic membrane pollution and cleaning in advanced treatment and recycling of municipal sewage treatment by a membrane method.
Description
Technical Field
The invention belongs to the technical field of membrane surface modification and membrane pollution cleaning, and particularly relates to a molybdenum disulfide composite membrane, and a preparation method, a cleaning method and application thereof.
Background
The membrane separation technology is widely applied to industrial wastewater treatment, advanced sewage treatment and drinking water treatment by virtue of the advantages of high separation efficiency, simple and convenient operation, small occupied area and the like. The basis of the membrane separation technology is various filter membranes which are made of inorganic materials or organic polymer materials and have porous structures, so that the effect of intercepting certain pore-size pollutants is achieved. The ultrafiltration membrane can effectively remove microorganisms such as algae, bacteria, protozoa, viruses and the like in the water body, greatly improves the biological stability of the effluent, and has obvious optimization effects on advanced sewage treatment and drinking water treatment. In addition, the ultrafiltration membrane can also effectively remove macromolecular particles and macromolecular organic polymers in water.
Ultrafiltration membranes are of a wide variety and are mainly classified into inorganic membranes and organic membranes. The inorganic membrane has the advantages of chemical corrosion resistance, wide suitable temperature, large mechanical strength, high pollution resistance and the like, is mainly applied to sewage treatment, but has the manufacturing cost far higher than that of the organic membrane; the organic film is mainly made of organic polymers, has low manufacturing cost and is widely popularized in industrial production. Organic membrane materials are broadly classified into four types, cellulose, polysulfone, vinyl and fluorine, and Cellulose Acetate (CA), Polyethersulfone (PES), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF) and polyvinyl chloride (PVC) are the most commonly used organic membrane materials. The PES ultrafiltration membrane has excellent performances of mechanical stability, chemical stability, corrosion resistance, oxidation resistance, organic solvent resistance and the like, so that the PES ultrafiltration membrane is rapidly developed and widely applied in the field of sewage treatment in recent years. However, with the long-term operation of membrane filtration, the membrane pollution seriously affects the membrane filtration process, not only increases the membrane filtration resistance, reduces the flux and increases the operation energy consumption, but also more importantly influences the operation stability of the process and threatens the process safety.
The membrane cleaning is to clean and regenerate the polluted membrane by adopting a reasonable cleaning method, destroy a solute adsorption layer on the surface of the membrane, remove impurities in a membrane pore passage and recover the membrane to the initial flux as far as possible. The membrane cleaning method may be classified into a physical cleaning method and a chemical cleaning method. The physical cleaning comprises hydraulic cleaning, gas pulse cleaning, ultrasonic cleaning and the like, can well remove pollutants on the surface of the membrane, but cannot remove pollutants in the pore channel of the membrane, and has poor cleaning effect. Chemical cleaning is to achieve the effects of loosening, dissolving dirt, oxidizing organic matters and inactivating microorganisms to remove membrane pollution by using chemical agents; the common cleaning method comprises acid washing, alkali washing, alcohol washing and oxidizing agents (such as ozone, hypochlorous acid, potassium permanganate and the like), the membrane pollution can be remarkably relieved by cleaning the membrane pollution through oxidation reaction, the removal effect of pollutants such as organic matters and the like can be improved, but the ultrafiltration membrane is easy to be damaged to a certain degree, and the membrane performance is influenced.
Disclosure of Invention
The invention provides a molybdenum disulfide composite membrane, a preparation method, a cleaning method and application thereof, aiming at the technical problems in the prior art, the prepared molybdenum disulfide composite membrane has excellent catalytic performance, good mechanical performance and very obvious membrane cleaning effect, and can better solve the problems of organic matter membrane pollution and cleaning in advanced treatment and recycling of municipal sewage treatment by a membrane method.
The technical scheme adopted by the invention is as follows: a preparation method of a molybdenum disulfide composite film comprises the following steps:
step A, ultrafiltration membrane pretreatment: soaking a flat plate polyether sulfone membrane in ultrapure water for 24 hours;
step B, preparing molybdenum disulfide dispersion liquid: adding molybdenum disulfide into ultrapure water, and uniformly dispersing by ultrasonic to obtain a molybdenum disulfide dispersion liquid with the concentration of 0.25-0.35 g/L;
step C, functional layer preparation: taking the flat polyether sulfone membrane out of the ultrapure water, washing the surface of the membrane with the ultrapure water, then installing the membrane at the bottom end of an ultrafiltration cup, pouring the molybdenum disulfide dispersion liquid into the ultrafiltration cup, filtering under the constant pressure of 0.3MPa, taking out the membrane after the filtration is finished, and washing the surface of the membrane with the ultrapure water to remove a small amount of loose molybdenum disulfide on the surface.
Further, in the step B, ultrasonic dispersion is carried out for 5-10 min.
Further, in the step B, the concentration of the molybdenum disulfide dispersion liquid is 0.35 g/L.
Further, the preparation method of molybdenum disulfide in the step B comprises the following steps:
step a, pouring thiourea and ammonium molybdate into ultrapure water, placing the ultrapure water on a magnetic stirrer, and stirring the ultrapure water and the ammonium molybdate for 35min at a speed of 300r/min to form a homogeneous solution;
b, transferring the stirred homogeneous solution into a stainless steel high-pressure reaction kettle with a Teflon lining, and heating for 24 hours in an oven at 180 ℃;
and c, cooling, collecting the product in the stainless steel high-pressure reaction kettle, centrifuging for 5min at 3000r/min, washing for 3 times by using ultrapure water, washing for 3 times by using absolute ethyl alcohol, washing for 3 times by using ultrapure water, placing the product in a vessel, drying for 12h at the temperature of 60 ℃ in an oven, and grinding into powder to obtain the molybdenum disulfide.
The technical scheme adopted by the invention is as follows: the molybdenum disulfide composite membrane prepared by the preparation method.
The technical scheme adopted by the invention is as follows: the molybdenum disulfide composite membrane is applied to entrapping organic macromolecules in water.
The technical scheme adopted by the invention is as follows: the cleaning method of the molybdenum disulfide composite membrane comprises the following steps:
s1, preparing a membrane cleaning solution: hydrogen peroxide solution with the mass fraction of 1 percent is used for adjusting the pH value to 4.0 by HCl solution;
s2, membrane cleaning process: and putting the polluted molybdenum disulfide composite membrane into a prepared hydrogen peroxide solution, carrying out cleaning reaction for 5min at a speed of 50r/min in a shaking table, taking out the membrane, washing the surface of the membrane by using ultrapure water, and removing the residual hydrogen peroxide cleaning agent on the surface.
Further, in step S2, the molybdenum disulfide composite membrane is placed into the prepared hydrogen peroxide solution with its load surface facing upward.
The technical scheme adopted by the invention is as follows: the cleaning method of the molybdenum disulfide composite membrane is applied to sewage treatment and regeneration.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes molybdenum disulfide dispersion liquid with peroxidase-like characteristics as a material, prepares a molybdenum disulfide functional layer on the surface of an ultrafiltration membrane in a pressure-assisted filtration assembly mode, triggers the in-situ catalysis function of the functional layer and a membrane cleaning medicament hydrogen peroxide by utilizing the internal relation between the functional layer and the membrane cleaning medicament hydrogen peroxide, and generates strong oxidizing free radicals and oxygen, thereby degrading pollutants on the surface of the membrane.
2. The method can remove most of hydrophobic humic acid pollutants on the composite membrane, effectively recover the water flux of the composite membrane, and has the advantages of economic operation method, easy operation and larger application prospect.
3. The main materials of the polyether sulfone ultrafiltration membrane are molybdenum disulfide and hydrogen peroxide, the molybdenum disulfide nano material is simple to prepare, low in cost and large in specific surface area, the catalytic capability of the polyether sulfone ultrafiltration membrane is enhanced due to the exposure of high-density active edges, the prepared catalytic material is attached to the surface of the polyether sulfone ultrafiltration membrane and can be fully contacted and reacted in a hydrogen peroxide cleaning solution, the generated free radicals are firstly contacted and reacted with humic acid, the polyether sulfone base membrane is prevented from being exposed in an oxidation environment, and therefore the damage of the hydrogen peroxide and the generated free radicals to the polyether sulfone base membrane is reduced.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention;
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Examples
The embodiment of the invention provides a preparation method and a cleaning method of a molybdenum disulfide composite membrane, as shown in figure 1, the preparation method comprises the following steps:
the method comprises the following steps: preparation of molybdenum disulfide material
1.1, weighing 1.96g of thiourea and 1.064g of ammonium molybdate, pouring the weighed materials into a beaker containing 30ml of ultrapure water, placing the beaker on a magnetic stirrer, and violently stirring the beaker for 35min at the speed of 300r/min to form a homogeneous solution;
1.2, transferring the stirred homogeneous solution into a stainless steel high-pressure reaction kettle with a capacity of 100ml and a Teflon lining, and heating for 24 hours in an oven at 180 ℃;
1.3, collecting the obtained product after cooling, centrifuging for 5min at 3000r/min, washing for 3 times by using ultrapure water, washing for 3 times by using absolute ethyl alcohol, washing for 3 times by using ultrapure water, placing the product in a vessel, and drying for 12h at the temperature of 60 ℃ in an oven. Grinding into powder, drying and storing.
Step two: PES ultrafiltration membrane pretreatment
2. A flat polyethersulfone membrane (PES, molecular cut-off: 30Kda) was cut into a circular sheet having a diameter of 50mm and an effective filtration area of 12.56cm 2 The membrane was soaked in ultrapure water for 24h with the smooth side facing down.
Step three: preparation molybdenum disulfide composite film
3.1, weighing 35mg of the molybdenum disulfide powder prepared in the first step, adding the molybdenum disulfide powder into a beaker containing 100ml of ultrapure water, and uniformly dispersing by ultrasonic for 5-10 min to obtain a molybdenum disulfide dispersion liquid.
3.2, taking out the flat polyethersulfone membrane soaked for 24 hours, washing the surface of the membrane with ultrapure water, then installing the membrane at the bottom end of an ultrafiltration cup, pouring the prepared molybdenum disulfide dispersion liquid into the ultrafiltration cup, filtering under the constant pressure of 0.3Mpa, and continuing to press for 5-10 min after the filtration is finished. Taking out and washing the surface of the membrane by ultrapure water, and removing a small amount of loose molybdenum disulfide on the surface.
Step four: humic acid polluted molybdenum disulfide composite film
4.1, weighing 0.5g of humic acid and 1g of sodium hydroxide, pouring the humic acid and the sodium hydroxide into a beaker containing 200ml of distilled water, magnetically stirring for 2 hours, and transferring the humic acid into a 500ml volumetric flask for constant volume after the humic acid is completely dissolved to prepare 1g/L humic acid stock solution. Taking 4ml of humic acid stock solution, adding distilled water to a constant volume of 400ml, and adjusting the pH to 7.0 by using 1mol and 0.1mol of HCl solution to obtain 10mg/L humic acid solution.
4.2, installing the molybdenum disulfide composite membrane prepared in the third step at the bottom of the ultrafiltration cup, filtering ultrapure water under the constant pressure of 0.1Mpa until the water flux is stable at the same time interval, and recording and calculating the initial flux of the molybdenum disulfide composite membrane. 350ml of 10mg/L humic acid solution is added, the humic acid pollution is carried out for 3h under the constant pressure of 0.1Mpa (pressure supply is carried out by depending on the nitrogen pressure), and the flux at the end time of the humic acid pollution is recorded and calculated.
Repeating the step for 4.2 times to respectively obtain a 1# molybdenum disulfide composite film, a 2# molybdenum disulfide composite film and a 3# molybdenum disulfide composite film after humic acid pollution; and (3) respectively carrying out water flux tests on the 1# molybdenum disulfide composite membrane, the 2# molybdenum disulfide composite membrane and the 3# molybdenum disulfide composite membrane by using ultrapure water, wherein the obtained water fluxes are respectively 50.14LMH/bar, 52.52LMH/bar and 47.45LMH/bar, the concentrations of humic acid of the stock solution and the percolate are measured, and the calculated retention rates are respectively 90.47%, 92.01% and 91.16%.
Step five: hydrogen peroxide cleaning molybdenum disulfide composite film
5.1, transferring 3ml (30%) of hydrogen peroxide solution, setting the volume of distilled water to 90ml (1%) of hydrogen peroxide solution, and adjusting the pH value to 4.0 by using 0.1mol of HCl solution.
And 5.2, taking out the molybdenum disulfide composite membrane polluted by the humic acid in the step four, washing the surface of the membrane by using ultrapure water, removing redundant humic acid on the surface, filtering the ultrapure water under the constant pressure of 0.1Mpa until the water flux is stable at the same time interval, and recording and calculating the flux of the molybdenum disulfide composite membrane 1#, the molybdenum disulfide composite membrane 2# and the molybdenum disulfide composite membrane 3 which are subjected to reversible pollution removal by using the ultrapure water after the humic acid is polluted to be 78.78LMH/bar, 81.17LMH/bar and 74.01LMH/bar respectively.
And respectively soaking the load surfaces of the 1# molybdenum disulfide composite membrane, the 2# molybdenum disulfide composite membrane and the 3# molybdenum disulfide composite membrane into the prepared hydrogen peroxide solution with the load surfaces facing upwards, and cleaning and reacting for 5min at the speed of 50r/min in a shaking table. And after the cleaning is finished, taking out the membrane, and washing the surface of the membrane by using ultrapure water to remove the residual hydrogen peroxide cleaning agent on the surface. And (3) mounting the cleaned membrane at the bottom of an ultrafiltration cup, filtering ultrapure water under the constant pressure of 0.1Mpa until the water flux is stable at the same time interval, and respectively recording and calculating the flux of the 1# molybdenum disulfide composite membrane, the 2# molybdenum disulfide composite membrane and the 3# molybdenum disulfide composite membrane after being cleaned by hydrogen peroxide as 101.46LMH/bar, 102.66LMH/bar and 95.50 LMH/bar.
According to the embodiment, the 1# molybdenum disulfide composite membrane, the 2# molybdenum disulfide composite membrane and the 3# molybdenum disulfide composite membrane polluted by humic acid are placed in hydrogen peroxide cleaning liquid to be soaked for 5min, and then the surfaces of the composite membranes are washed by ultrapure water, the water fluxes of the 1# molybdenum disulfide composite membrane, the 2# molybdenum disulfide composite membrane and the 3# molybdenum disulfide composite membrane washed by the ultrapure water are 101.46LMH/bar, 102.66LMH/bar and 95.50LMH/bar respectively, compared with the initial water flux of the prepared molybdenum disulfide composite membrane of 108.23 +/-4.97 LMH/bar, the flux recovery rate reaches about 75%, and the result shows that the water flux recovery rate of the molybdenum disulfide composite membrane washed by hydrogen peroxide is high; and the retention rates of the raw solution and the percolate obtained from the molybdenum disulfide composite membrane in the humic acid pollution process are respectively 90.47%, 92.01% and 91.16%.
Comparative examples
Step one, humic acid polluted polyethersulfone ultrafiltration membrane
And (3) installing the polyethersulfone ultrafiltration membrane pretreated in the second step in the embodiment at the bottom of the ultrafiltration cup, filtering ultrapure water under the constant pressure of 0.1MPa until the water flux is stable at the same time interval, and recording and calculating the initial flux of the polyethersulfone ultrafiltration membrane. Adding 350ml of 10mg/L humic acid solution prepared in the step 4.1 in the embodiment, carrying out humic acid pollution for 3h under the constant pressure of 0.1MPa (pressure supply is carried out by depending on nitrogen pressure), obtaining the polyether sulfone ultrafiltration membrane attached with humic acid when the humic acid blocks the membrane pores of the polyether sulfone ultrafiltration membrane and the humic acid forms cakes, and recording and calculating the flux at the end of the humic acid pollution.
Repeating the steps for three times to respectively obtain a 1# polyethersulfone ultrafiltration membrane, a 2# polyethersulfone ultrafiltration membrane and a 3# polyethersulfone ultrafiltration membrane which are polluted by humic acid; and respectively carrying out water flux tests on the 1# polyethersulfone ultrafiltration membrane, the 2# polyethersulfone ultrafiltration membrane and the 3# polyethersulfone ultrafiltration membrane by using ultrapure water to obtain water fluxes of 64.46LMH/bar, 62.07LMH/bar and 60.49LMH/bar respectively, and measuring the retention rates of the stock solution and the percolate to be 85.02%, 82.57% and 83.98% respectively.
Step two, cleaning the polyethersulfone ultrafiltration membrane by hydrogen peroxide
Taking out the polyether sulfone ultrafiltration membrane polluted by the humic acid, washing the surface of the membrane by using ultrapure water, removing redundant humic acid on the surface, filtering the ultrapure water under the constant pressure of 0.1MPa until the water flux is stable at the same time interval, and recording and calculating the flux of the 1# polyether sulfone ultrafiltration membrane, the 2# polyether sulfone ultrafiltration membrane and the 3# polyether sulfone ultrafiltration membrane subjected to reversible pollution removal after the humic acid is polluted to be 85.95LMH/bar, 83.56LMH/bar and 78.78LMH/bar respectively.
And then respectively soaking the 1# polyethersulfone ultrafiltration membrane, the 2# polyethersulfone ultrafiltration membrane and the 3# polyethersulfone ultrafiltration membrane which are polluted by the humic acid into the hydrogen peroxide solution prepared in the step 5.1 in the embodiment with the loading surfaces facing upwards, and cleaning and reacting for 5min in a shaking table at the speed of 50 r/min. And after the cleaning is finished, taking out the film, washing the surface of the film again by using ultrapure water, and removing the residual hydrogen peroxide cleaning agent on the surface. And (3) mounting the cleaned membrane at the bottom of an ultrafiltration cup, filtering ultrapure water under the constant pressure of 0.1MPa until the water flux is stable at the same time interval, and respectively recording and calculating the flux of the 1# polyethersulfone ultrafiltration membrane, the 2# polyethersulfone ultrafiltration membrane and the 3# polyethersulfone ultrafiltration membrane after being cleaned by hydrogen peroxide as 89.53LMH/bar, 88.33LMH/bar and 82.37 LMH/bar.
The comparative example shows that the polyethersulfone ultrafiltration membrane 1# polluted by humic acid, the polyethersulfone ultrafiltration membrane 2# polluted by humic acid and the polyethersulfone ultrafiltration membrane 3# polluted by humic acid are placed in hydrogen peroxide cleaning solution to be soaked for 5min and then the surfaces of the polyethersulfone ultrafiltration membrane 1# polluted by humic acid, the polyethersulfone ultrafiltration membrane 2# polluted by humic acid and the polyethersulfone ultrafiltration membrane 3# polluted by humic acid are washed by ultrapure water, the water fluxes of the polyethersulfone ultrafiltration membrane 1# polluted by ultrapure water, the polyethersulfone ultrafiltration membrane 2# polluted by humic acid and the polyethersulfone ultrafiltration membrane 3# polluted by humic acid are 89.53LMH/bar, 88.33LMH/bar and 82.37LMH/bar respectively, the initial water flux of the polyethersulfone ultrafiltration membrane prepared by the ultrapure water is 112.21 +/-2.39 LMH/bar, the flux recovery rate is only 15%, and the water flux recovery of the polyethersulfone ultrafiltration membrane washed by hydrogen peroxide is poor; and the rejection rates of raw liquid and percolate obtained from the polyether sulfone ultrafiltration membrane in the humic acid pollution process are respectively 85.02%, 82.57% and 83.98%.
The media for testing the water flux in the above examples and comparative examples are all ultrapure water, and the method for testing the water flux is to pour the ultrapure water into an ultrafiltration cup provided with a membrane, and measure the ultrapure water by the pore diameter filtration of a molybdenum disulfide composite membrane or a polyether sulfone ultrafiltration membrane under the constant pressure of 0.1MPa, and the ultrapure water is not influenced by other external forces.
The embodiment and the comparative example show that the water flux recovery of the molybdenum disulfide composite membrane after being cleaned by hydrogen peroxide for 5min is about 5 times that of a polyether sulfone ultrafiltration membrane, the retention rate of the molybdenum disulfide composite membrane is higher than that of the polyether sulfone ultrafiltration membrane, and the retention effect is more prominent.
Table 1: membrane flux data sheet (LMH/bar)
Table 1 shows the water flux test results of the 1# molybdenum disulfide composite film, the 2# molybdenum disulfide composite film and the 3# molybdenum disulfide composite film; and the water flux test results of the No. 1 polyethersulfone ultrafiltration membrane, the No. 2 polyethersulfone ultrafiltration membrane and the No. 3 polyethersulfone ultrafiltration membrane.
Table 2: data sheet of membrane rejection
Table 2 shows retention rate test results of the 1# molybdenum disulfide composite film, the 2# molybdenum disulfide composite film, and the 3# molybdenum disulfide composite film; and the retention rate test results of the No. 1 polyethersulfone ultrafiltration membrane, the No. 2 polyethersulfone ultrafiltration membrane and the No. 3 polyethersulfone ultrafiltration membrane.
It can be concluded from the above examples and comparative examples that: after the molybdenum disulfide composite membrane is soaked in hydrogen peroxide cleaning solution and cleaned for 5min, the water flux recovery of the molybdenum disulfide composite membrane reaches about 75%, and the water flux recovery of the polyether sulfone ultrafiltration membrane under the same conditions is only 15%. Hydrogen peroxide is independently used for cleaning, the number of generated free radicals is very limited, and the recovery rate of water flux after the polyether sulfone ultrafiltration membrane is cleaned is low; the molybdenum disulfide loaded on the surface of the molybdenum disulfide composite membrane has the characteristic of peroxidase-like activity, and the in-situ cleaning functional layer and hydrogen peroxide serving as a membrane cleaning agent are internally linked to trigger the in-situ catalysis function of the molybdenum disulfide composite membrane, so that a large amount of strong-oxidizing free radicals and oxygen are generated, pollutants on the surface of the membrane are degraded to a great extent, the self-cleaning function of the surface of the membrane is realized, and the flux recovery rate of the membrane is greatly improved. The composite membrane prepared by the molybdenum disulfide functional layer is constructed on the surface of the polyether sulfone ultrafiltration membrane, so that pollutants can be better intercepted, and the membrane interception efficiency is improved. In subsequent experiments, compared with a polyether sulfone ultrafiltration membrane, the molybdenum disulfide composite membrane has very good stability under the condition of long-term continuous use; and the molybdenum disulfide functional layer is constructed, so that the damage of a hydrogen peroxide oxidant to the base membrane can be avoided, and the service life of the ultrafiltration membrane is prolonged.
The present invention has been described in detail with reference to the embodiments, but the description is only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The scope of protection of the invention is defined by the claims. The technical solutions of the present invention or those skilled in the art, based on the teachings of the technical solutions of the present invention, should be within the scope of the present invention, and the claims of the present invention should also cover the scope of the present invention by designing similar technical solutions to achieve the above technical effects or by making equivalent changes and improvements in the scope of the present invention.
Claims (9)
1. A preparation method of a molybdenum disulfide composite film is characterized by comprising the following steps: the method comprises the following steps:
step A, ultrafiltration membrane pretreatment: soaking a flat plate polyether sulfone membrane in ultrapure water for 24 hours;
step B, preparing molybdenum disulfide dispersion liquid: adding molybdenum disulfide into ultrapure water, and uniformly dispersing by using ultrasonic to obtain a molybdenum disulfide dispersion liquid with the concentration of 0.25-0.35 g/L;
step C, functional layer preparation: taking the flat polyether sulfone membrane out of the ultrapure water, washing the surface of the membrane with the ultrapure water, then installing the membrane at the bottom end of an ultrafiltration cup, pouring the molybdenum disulfide dispersion liquid into the ultrafiltration cup, filtering under the constant pressure of 0.3MPa, taking out the membrane after the filtration is finished, and washing the surface of the membrane with the ultrapure water.
2. The method for preparing the molybdenum disulfide composite film according to claim 1, wherein: and in the step B, ultrasonic dispersion is carried out for 5-10 min.
3. The method for preparing the molybdenum disulfide composite film according to claim 1, wherein: in the step B, the concentration of the molybdenum disulfide dispersion liquid is 0.35 g/L.
4. The method for preparing the molybdenum disulfide composite film according to claim 1, wherein: the preparation method of the molybdenum disulfide in the step B comprises the following steps:
step a, pouring thiourea and ammonium molybdate into ultrapure water, placing the ultrapure water on a magnetic stirrer, and stirring the ultrapure water and the ammonium molybdate for 35min at a speed of 300r/min to form a homogeneous solution;
b, transferring the stirred homogeneous solution into a stainless steel high-pressure reaction kettle with a Teflon lining, and heating for 24 hours in an oven at 180 ℃;
and step c, collecting products in the stainless steel high-pressure reaction kettle after cooling, centrifuging for 5min at 3000r/min, washing for 3 times by using ultrapure water, washing for 3 times by using absolute ethyl alcohol, washing for 3 times by using ultrapure water, placing the products in a vessel, drying for 12h at the temperature of 60 ℃ in an oven, and grinding into powder to obtain the molybdenum disulfide.
5. A molybdenum disulfide composite film produced by the method for producing a molybdenum disulfide composite film according to any one of claims 1 to 4.
6. The molybdenum disulfide composite membrane of claim 5 applied to entrap organic macromolecules in water.
7. A cleaning method of a molybdenum disulfide composite membrane is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a membrane cleaning solution: hydrogen peroxide solution with the mass fraction of 1 percent is used for adjusting the pH value to 4.0 by HCl solution;
s2, membrane cleaning process: and putting the polluted molybdenum disulfide composite membrane into a prepared hydrogen peroxide solution, carrying out cleaning reaction for 5min at a speed of 50r/min in a shaking table, taking out the membrane, and washing the surface of the membrane by using ultrapure water.
8. The method for preparing the molybdenum disulfide composite film according to claim 7, wherein: in the step S2, the load surface of the molybdenum disulfide composite membrane faces upward, and the molybdenum disulfide composite membrane is placed in the prepared hydrogen peroxide solution.
9. The cleaning method of the molybdenum disulfide composite membrane according to claim 7 or 8, which is applied to sewage treatment and regeneration.
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