CN116672894A - MXene doped photothermal distillation membrane and preparation method and application thereof - Google Patents
MXene doped photothermal distillation membrane and preparation method and application thereof Download PDFInfo
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- 238000004821 distillation Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000000463 material Substances 0.000 claims abstract description 39
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000002131 composite material Substances 0.000 claims description 64
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
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- 238000003756 stirring Methods 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007853 buffer solution Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 12
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- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001291 vacuum drying Methods 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
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- 238000009736 wetting Methods 0.000 abstract description 4
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- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000010612 desalination reaction Methods 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000002585 base Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 3
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- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000003486 chemical etching Methods 0.000 description 2
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- 150000003624 transition metals Chemical class 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D71/26—Polyalkenes
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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
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- 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
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of separation membranes, and particularly relates to an MXene doped photothermal distillation membrane, and a preparation method and application thereof. Aiming at the defects of obvious temperature polarization, low flux and easy pollution and wetting in the existing membrane distillation technology, the invention is based on the excellent photo-thermal conversion efficiency and pollution resistance of MXene, and the MXene is compounded with hydrophilic materials such as graphene oxide, polymerized dopamine, chitosan and the like and then deposited on the surface of a hydrophobic microporous membrane to form a photo-thermal compound layer, so that the compound membrane has a surface-layer hydrophilic-bottom hydrophobic double-layer structure, has higher photo-thermal conversion efficiency, higher pollutant interception efficiency and stable permeation flux when the salt-containing organic wastewater is treated, can realize the synchronous improvement of indexes such as photo-thermal membrane distillation heat efficiency, pollution resistance, permeation flux and the like, and has wide application prospect in the aspects of membrane distillation treatment of wastewater and seawater desalination.
Description
Technical Field
The invention belongs to the technical field of separation membranes, and particularly relates to an MXene doped photothermal distillation membrane, and a preparation method and application thereof.
Background
The membrane distillation technology heats the inlet water and cools the produced water at the same time so as to generate steam pressure difference at two sides of the hydrophobic microporous membrane, and the water molecules in the wastewater are pushed to pass through the microporous membrane in a gaseous form and are condensed and recovered at the other side. Compared with the membrane separation process driven by reverse osmosis and the like, the membrane distillation can be operated at normal pressure, has strong adaptability to waste water and high water output quality, can utilize low-grade heat sources such as industrial waste heat and the like to drive the membrane separation process, and has good application potential in the aspects of recycling high-salt organic waste water and near zero emission of industrial waste water.
However, because the membrane distillation process requires the water molecules to generate gas-liquid phase transition on the surface of the membrane, obvious temperature polarization phenomenon can be generated, so that the thermal efficiency of the membrane distillation is low and the water production flux is not high. The research and development application of the photo-thermal distillation membrane are beneficial to overcoming temperature polarization and improving the distillation heat efficiency of the membrane, and at present, photo-thermal materials such as noble metal, carbon nano tube, graphene and the like with hydrophobic characteristics are commonly used for being loaded on the surface of the membrane to form a photo-thermal layer, but the deposition of the hydrophobic photo-thermal materials on the surface of the membrane can increase mass transfer resistance, so that flux is reduced, the photo-thermal conversion efficiency of the distillation membrane is relatively low, and the photo-thermal conversion efficiency of the distillation membrane is expected to be remarkably improved by introducing more efficient photo-thermal materials.
On the other hand, the high-salt organic wastewater has high pollutant concentration and complex components, so that serious membrane pollution is generated in the membrane distillation process, the membrane distillation flux decays faster, and the traditional photo-thermal material can absorb pollutants in the wastewater to aggravate the membrane pollution or cause membrane wetting, so that the flux and pollutant interception efficiency of the membrane distillation are reduced when the wastewater is treated, and the thermal efficiency, high flux and pollution resistance of the membrane distillation are difficult to realize at the same time, so that the improvement of the pollution resistance of the distillation membrane under the condition of local heating of the membrane surface has important significance for the development of the photo-thermal membrane distillation. Development of novel photo-thermal film materials is needed to realize synchronous improvement of photo-thermal conversion efficiency, permeation flux and anti-pollution performance.
Disclosure of Invention
The invention aims to provide a high-flux anti-pollution photo-thermal composite membrane for photo-thermal membrane distillation, aiming at the defects and defects of obvious temperature polarization, low flux and easiness in pollution and wetting in the existing membrane distillation technology. The photo-thermal composite membrane is based on the excellent photo-thermal conversion efficiency and pollution resistance of MXene, and the MXene is compounded with hydrophilic materials such as graphene oxide, polymerized dopamine and chitosan and then deposited on the surface of a hydrophobic microporous membrane to form a photo-thermal composite layer, so that the composite membrane has a surface layer hydrophilic-bottom layer hydrophobic double-layer structure, has higher photo-thermal conversion efficiency, has higher pollutant interception efficiency and stable permeation flux when treating salt-containing organic wastewater, can realize synchronous improvement of indexes such as distillation heat efficiency, pollution resistance, permeation flux and the like of the photo-thermal membrane, and has wide application prospect in the aspects of membrane distillation treatment of wastewater and seawater desalination.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the MXene doped photo-thermal distillation membrane has a double-layer structure that an MXene doped hydrophilic surface layer is combined with a hydrophobic bottom layer, wherein the MXene doped hydrophilic surface layer is a composite photo-thermal material of MXene and a hydrophilic polymer, and the hydrophobic bottom layer is a hydrophobic substrate membrane.
Further, the hydrophilic polymer is polydopamine, polyvinyl alcohol, polyethylene glycol, polyethyleneimine, graphene oxide, chitosan, sodium alginate, cellulose or a copolymer or a composition of the above substances.
MXene is a two-dimensional transition metal carbide or nitride of the formula M n+1 X n Wherein M represents a transition metal (e.g., sc, ti, zr, hf, V, nb, ta, cr and Mo), and X isCarbon or nitrogen element, n is a positive integer.
MXene can be made by fluoride or alkali etching of layered precursors of metal carbo/nitrides.
The preparation method of the MXene doped photothermal distillation membrane comprises the following steps:
step 1, preparing an MXene doped composite photo-thermal material: dissolving MXene and a hydrophilic polymer in deionized water for ultrasonic dispersion, adding dopamine hydrochloride, stirring at room temperature, adding Tris-HCl buffer solution, placing the mixed solution in water bath for stirring reaction, cooling to room temperature after the reaction is finished, and obtaining MXene doped composite photo-thermal material solid powder through centrifugation, washing and vacuum drying;
step 2, treatment of a hydrophobic base film: soaking a hydrophobic basal membrane in isopropanol, then soaking in deionized water, standing and airing, soaking the hydrophobic basal membrane soaked in isopropanol and deionized water in a Tris-HCl buffer solution of dopamine, stirring at room temperature for reaction, washing with deionized water for a plurality of times, and airing for later use;
step 3, preparation of an MXene doped photothermal distillation membrane: dissolving the solid powder of the MXene doped composite photo-thermal material obtained in the step 1 in deionized water for ultrasonic dispersion, then combining the solid powder with the surface of the hydrophobic substrate film treated in the step 2, washing the surface of the film with deionized water, and then immersing the film into absolute ethyl alcohol to remove the redundant MXene doped composite photo-thermal material, thus obtaining the MXene doped photo-thermal distillation film.
Further, in the step 1, the mass ratio of MXene to the hydrophilic polymer is 1-200:10, the hydrophilic polymer is polydopamine, polyvinyl alcohol, polyethylene glycol, polyethyleneimine, graphene oxide, chitosan, sodium alginate, cellulose and a copolymer or a composition of the above substances, and the mass ratio of dopamine hydrochloride to the MXene/hydrophilic polymer mixture is 1:1-5.
Further, the ultrasonic dispersion time in the step 1 is 0.5-2 h; stirring at room temperature for 05-2 h; the temperature of the water bath is 50-80 ℃; the stirring reaction time in the water bath is 1-2 h, and the stirring speed is 400-900 rpm; the centrifugation time is 10-20 min, and the rotating speed is 3000-5000 rpm; washing for more than 3 times.
Further, the concentration of the Tris-HCl buffer solution in the step 1 and the step 2 is 50mmol/L, the pH=8.5, and the concentration of the Tris-HCl buffer solution of the dopamine in the step 2 is 0.2-2 g/L.
Further, the hydrophobic substrate film in the step 2 is one of polytetrafluoroethylene, polyvinylidene fluoride and polypropylene.
Further, the isopropanol soaking time in the step 2 is 1-2 h, the deionized water soaking time is 6-14 h, the stirring reaction time is 1-24 h, and the washing is more than 3 times.
Further, the loading amount of the MXene doped composite photo-thermal material on the surface of the treated hydrophobic base film in the step 3 is 0.1-5 mg/cm 2 The method for combining the surface of the hydrophobic substrate film treated in the step 2 is one of spraying, film scraping, vacuum filtration, dip coating or electrostatic spinning.
Further, the ultrasonic treatment time in the step 3 is 1 to 6 hours.
The application of the MXene doped photothermal distillation membrane is applied to membrane distillation treatment of wastewater containing inorganic salts and/or organic matters.
Compared with the prior art, the invention has the following advantages:
in the invention, the photo-thermal composite film is prepared by doping hydrophilic materials such as MXene, graphene Oxide (GO), polydopamine (PDA), chitosan (CTS) and the like, the synergistic advantage of the composite material is exerted, and the prepared photo-thermal composite film has good stability, high photo-thermal efficiency and higher interception efficiency on most inorganic salts and organic matters; the hydrophilic-hydrophobic composite photo-thermal membrane prepared by utilizing the excellent photo-thermal conversion characteristics and hydrophilicity of MXene, GO, PDA and other materials can realize synchronous improvement of the thermal efficiency, pollution resistance and permeation flux of membrane distillation; meanwhile, the preparation process of the photo-thermal distillation film is simple, the conditions are mild, and the application of the photo-thermal distillation film is widened.
Drawings
FIG. 1 is a schematic illustration of a process for preparing an MXene doped photothermal distillation membrane;
FIG. 2 is an SEM image of an MXene/GO/PDA composite photo-thermal material;
FIG. 3 is a SEM cross-sectional view of the surface of an MXene doped photothermal distillation membrane;
FIG. 4 is a graph showing the contact angle of the surface of an MXene doped photothermal distillation film with water;
FIG. 5 is a schematic diagram of a photothermal membrane distillation system;
FIG. 6 is a photo-thermal performance map of a MXene/GO/PDA composite distillation membrane.
Detailed Description
Example 1
As shown in fig. 1, a method for preparing an MXene doped photothermal distillation film includes the following steps:
step 1, preparing an MXene doped composite photo-thermal material:
will be 1g Ti 3 AlC 2 The powder was slowly added to 10mL of HCl solution containing 1g of LiF at 9mol/L for chemical etching, magnetically stirred in a water bath at 35℃for 20 hours, then washed with deionized water, centrifugally washed at 3500rpm to a pH of about 6, and the precipitate was dried in vacuo to obtain MXene.
MXene and Graphene Oxide (GO) were combined at 1:3, then adding dopamine hydrochloride, stirring for 1h at room temperature, adding Tris-HCl buffer solution with pH=8.5 and concentration of 50mmol/L, placing the mixed solution in a water bath at 60 ℃ at the rotating speed of 600rpm, stirring for 12h, cooling to room temperature after the reaction is finished, centrifuging for 15min at the rotating speed of 4000rpm, washing for more than 3 times, and vacuum drying to obtain the solid powder of the MXene doped composite photo-thermal material, wherein the surface morphology of the solid powder is shown in figure 2.
Step 2, treatment of a hydrophobic base film:
firstly, soaking a polyvinylidene fluoride (PVDF) hydrophobic basal membrane in isopropanol for 1h, then soaking the membrane in deionized water for 12h, standing and airing, soaking the hydrophobic basal membrane soaked in isopropanol and deionized water in Tris-HCl buffer solution (50 mmol/L, pH=8.5) with the concentration of 1g/L of dopamine, stirring and reacting for 12h at room temperature, then washing the membrane with deionized water for more than 3 times, and airing for later use.
Step 3, preparation of an MXene doped photothermal distillation membrane:
dissolving the solid powder of the MXene doped composite photo-thermal material obtained in the step 1 in deionized water, performing ultrasonic dispersion for 2 hours, and then combining the composite material on the surface of the hydrophobic substrate film treated in the step 2 by a vacuum suction filtration method, wherein the loading amount of the MXene doped composite photo-thermal material on the surface of the treated hydrophobic substrate film is 3.5mg/cm 2 And then washing the surface of the membrane by deionized water, immersing the membrane into absolute ethyl alcohol to remove redundant MXene doped composite photo-thermal material, thus obtaining the MXene doped photo-thermal distillation membrane, the cross section morphology of which is shown in figure 3, and the MXene doped composite photo-thermal material can be seen to be combined on the surface layer of the PVDF substrate. The hydrophilic-hydrophobic performance test of the membrane surface shows that the contact angle of the original hydrophobic PVDF substrate membrane and water is 119.8 degrees, the contact angle of the membrane surface and water after the MXene composite material is loaded is shown in figure 4, the contact angle is obviously reduced to 68.7 degrees, and the surface layer of the composite membrane has hydrophilicity, so that a surface layer hydrophilic-bottom layer hydrophobic double-layer composite membrane structure is formed.
Example 2
A preparation method of an MXene doped photothermal distillation membrane comprises the following steps:
step 1, preparing an MXene doped composite photo-thermal material:
will be 1g Ti 3 AlC 2 The powder was slowly added to 10mL of 50wt% hydrofluoric acid (HF) solution, stirred and etched in a water bath at 25℃for 24 hours, then washed with deionized water, centrifugally washed at 3000rpm to a pH of about 6, and the precipitate was dried in vacuo to obtain MXene.
Dissolving MXene and Chitosan (CTS) in deionized water according to a mass ratio of 20:1, performing ultrasonic dispersion for 2 hours, adding dopamine hydrochloride to enable the mass ratio of the dopamine hydrochloride to the MXene/CTS mixture to be 1:1, stirring for 2 hours at room temperature, adding a Tris-HCl buffer solution with pH of 8.5 and a concentration of 50mmol/L, placing the mixed solution into a water bath with the temperature of 80 ℃, stirring and reacting for 24 hours at the rotating speed of 400rpm, cooling to the room temperature after the reaction is finished, centrifuging for 10 minutes at the rotating speed of 5000rpm, washing for more than 3 times, and performing vacuum drying to obtain the MXene doped composite photo-thermal material solid powder.
Step 2, treatment of a hydrophobic base film:
firstly, soaking a Polytetrafluoroethylene (PTFE) hydrophobic basal membrane in isopropanol for 1.5h, then soaking the hydrophobic basal membrane in deionized water for 14h, standing and airing, soaking the hydrophobic basal membrane soaked in isopropanol and deionized water in Tris-HCl buffer solution (50 mmol/L, pH=8.5) with the concentration of 0.2g/L of dopamine, stirring and reacting for 24h at room temperature, then washing the hydrophobic basal membrane with deionized water for more than 3 times, and airing for later use.
Step 3, preparation of a photo-thermal distillation film:
dissolving the solid powder of the MXene doped composite photo-thermal material obtained in the step 1 in deionized water, performing ultrasonic dispersion for 1h, and then combining the composite material on the surface of the hydrophobic base film treated in the step 2 through a scratch film method, wherein the loading capacity of the MXene doped composite photo-thermal material on the surface of the treated hydrophobic base film is 5mg/cm 2 And then washing the surface of the membrane by deionized water, and immersing the membrane into absolute ethyl alcohol to remove redundant MXene doped composite photo-thermal materials, thus obtaining the MXene doped photo-thermal distillation membrane. The hydrophilic-hydrophobic performance test of the film surface shows that the contact angle between the MXene doped photothermal distillation film surface and water is 66.5 DEG
Example 3
A preparation method of an MXene doped photothermal distillation membrane comprises the following steps:
step 1, preparing an MXene doped composite photo-thermal material:
will be 1g Ti 3 AlC 2 The powder was slowly added to 10mL of HCl solution containing 1g of LiF at 9mol/L for chemical etching, then stirred in a water bath at 40℃for 16h, then washed with deionized water, centrifugally washed at 5000rpm to a pH of about 6, and the precipitate was dried in vacuo to obtain MXene.
MXene and polyvinyl alcohol (PVA) were combined at 1:10, then adding dopamine hydrochloride, stirring for 0.5h at room temperature, adding Tris-HCl buffer solution with pH=8.5 and 50mmol/L concentration, placing the mixed solution in a water bath at 50 ℃ and stirring for 2h at the rotating speed of 900rpm, cooling to room temperature after the reaction is finished, centrifuging for 20min at the rotating speed of 3000rpm, washing for more than 3 times, and vacuum drying to obtain the MXene doped composite photo-thermal material solid powder.
Step 2, treatment of a hydrophobic base film:
firstly, soaking a polypropylene (PP) hydrophobic basal membrane for 2 hours by isopropanol, then soaking the PP hydrophobic basal membrane in deionized water for 6 hours, standing and airing, then soaking the hydrophobic basal membrane soaked by isopropanol and deionized water in Tris-HCl buffer solution (50 mmol/L, pH=8.5) with the concentration of 2g/L of dopamine, stirring and reacting for 4 hours at room temperature, then washing the membrane with deionized water for more than 3 times, and airing for standby.
Step 3, preparation of a photo-thermal distillation film:
dissolving the solid powder of the MXene doped composite photo-thermal material obtained in the step 1 in deionized water, performing ultrasonic dispersion for 6 hours, and then combining the composite material on the surface of the hydrophobic substrate film treated in the step 2 by a spraying method, wherein the loading capacity of the MXene doped composite photo-thermal material on the surface of the treated hydrophobic substrate film is 0.5mg/cm 2 And then washing the surface of the membrane by deionized water, and immersing the membrane into absolute ethyl alcohol to remove redundant MXene doped composite photo-thermal materials, thus obtaining the MXene doped photo-thermal distillation membrane. The hydrophilic-hydrophobic performance test of the film surface shows that the contact angle between the MXene doped photothermal distillation film surface and water is 72.3 DEG
Example 4
The embodiment provides a method for treating salt-containing organic wastewater by membrane distillation by using an MXene doped photo-thermal composite membrane, which comprises the following specific steps:
the photo-thermal composite membrane in example 1 was used for membrane distillation treatment of wastewater containing 3000mg/L NaCl and 50mg/L humic acid, the circulation temperatures of the hot and cold sides of a photo-thermal membrane distillation system (shown in FIG. 5) were set to 20℃and 50℃respectively, the test results of the photo-thermal properties of the membrane surface of the composite membrane after 30s illumination under one solar illumination condition are shown in FIG. 6, the membrane surface temperature was raised to 57.6℃and the average water flux of membrane distillation was 30.7L/m 2 And h, compared with a single-layer PVDF hydrophobic membrane, the membrane is improved by 53%, and the salt interception rate is higher than 99.5%, which shows that the MXene doped photo-thermal composite membrane is beneficial to improving the membrane distillation flux and the pollutant interception performance.
Example 5
The embodiment provides a method for treating salt-containing organic wastewater by membrane distillation by using an MXene doped photo-thermal composite membrane, which comprises the following specific steps:
the photo-thermal composite membrane in the embodiment 1 is used for treating wastewater in an actual industrial park by membrane distillation, the COD concentration is 250-350 mg/L, the conductivity is 3.8-4.5 mS/cm, the circulating temperature of the cold and hot sides of a photo-thermal membrane distillation system is respectively set to 20 ℃ and 50 ℃, the photo-thermal membrane distillation experiment is carried out under the condition of sunlight, and the average water production flux is 28.5L/m 2 H, compared with a single-layer PVDF hydrophobic membrane, the trapping efficiency of the membrane is improved by 39%, and is higher than 99%, so that the MXene doped photo-thermal composite membrane has a good treatment effect on actual industrial wastewater.
Example 6
The embodiment provides a method for treating salt-containing organic wastewater by membrane distillation by using an MXene doped photo-thermal composite membrane, which comprises the following specific steps:
the photothermal composite membrane of example 2 was used for membrane distillation treatment containing CaSO 4 The circulating temperature of the cold and hot sides of a photo-thermal membrane distillation system is respectively set to be 20 ℃ and 50 ℃ under the condition of two solar lights, the surface temperature of a composite membrane is increased to 61.5 ℃ after 30s light is irradiated, and the average flux of membrane distillation is 36.4L/m 2 H, compared with a single-layer PTFE hydrophobic membrane, the water production rate is improved by 48%, and the water production rate is always kept below 5 mu S/cm, which shows that the MXene doped photo-thermal composite membrane has good flux improvement and anti-wetting performance.
Example 7
The embodiment provides a method for treating salt-containing organic wastewater by membrane distillation by using an MXene doped photo-thermal composite membrane, which comprises the following specific steps:
the photothermal composite membrane in example 3 was used for membrane distillation treatment of wastewater containing NaCl at 3000mg/L and mineral oil at 100mg/L, the circulation temperatures of the hot and cold sides of the photothermal membrane distillation system were set to 20℃and 40℃respectively, the surface temperature of the composite membrane was raised to 58.5℃after 60s illumination under two solar illumination conditions, and the average flux of membrane distillation was 16.7L/m 2 H, compared with a single-layer PP hydrophobic membrane, the trapping efficiency of the membrane on mineral oil is improved by 38%, and the trapping efficiency of the membrane on mineral oil is higher than 99.5%, which indicates that the photo-thermal composite membrane has good treatment effect on oily and salty wastewater.
Comparative example
The comparative example provides a preparation method of a GO/PDA composite membrane without MXene doping and application thereof in membrane distillation treatment of salt-containing organic wastewater, and the preparation method comprises the following specific steps:
and respectively soaking the PVDF hydrophobic basal membrane in isopropanol and deionized water for 1h and 12h, standing and airing, soaking in Tris-HCl buffer solution (50 mmol/L, pH=8.5) with the dopamine concentration of 1g/L, stirring at room temperature for reacting for 12h, washing with deionized water for more than 3 times, and airing for later use.
And carrying out ultrasonic treatment on 5mg/L of GO aqueous solution for 1h, combining GO on the surface of the dopamine-treated PVDF membrane by a membrane scraping method, washing the surface of the membrane by deionized water, and immersing the membrane into absolute ethyl alcohol to remove redundant GO, thereby obtaining the GO/PDA composite membrane without MXene doping.
The GO/PDA composite membrane is used for treating wastewater containing 3000mg/L NaCl and 50mg/L humic acid by membrane distillation, the circulating temperature of the cold side and the hot side of a membrane distillation system is respectively set to 20 ℃ and 50 ℃, the surface temperature of the composite membrane is not obviously changed when the composite membrane is irradiated for 30s under the condition of sunlight, and the average water yield of the membrane distillation is 22.6L/m 2 ·h。
The comparative test proves that the preparation method of the photo-thermal distillation membrane prepared by MXene doping is simple and has better photo-thermal performance, and the photo-thermal distillation membrane for membrane distillation treatment of high-salt organic wastewater has an anti-pollution effect of slowing down flux attenuation, so that the MXene doping photo-thermal distillation membrane used for wastewater treatment in the specification has good anti-pollution performance and is a material for saving energy and reducing consumption.
Claims (10)
1. The MXene doped photothermal distillation membrane is characterized by having a double-layer structure that a MXene doped hydrophilic surface layer is combined with a hydrophobic bottom layer, wherein the MXene doped hydrophilic surface layer is a composite photothermal material of MXene and a hydrophilic polymer, and the hydrophobic bottom layer is a hydrophobic base membrane.
2. The MXene doped photothermal distillation membrane according to claim 1, wherein said hydrophilic polymer is polydopamine, polyvinyl alcohol, polyethylene glycol, polyethylenimine, graphene oxide, chitosan, sodium alginate, cellulose and copolymers or combinations thereof.
3. A method of producing an MXene doped photothermal distillation membrane according to claim 1 or 2, comprising the steps of:
step 1, preparing an MXene doped composite photo-thermal material: dissolving MXene and a hydrophilic polymer in deionized water for ultrasonic dispersion, adding dopamine hydrochloride, stirring at room temperature, adding Tris-HCl buffer solution, placing the mixed solution in water bath for stirring reaction, cooling to room temperature after the reaction is finished, and obtaining MXene doped composite photo-thermal material solid powder through centrifugation, washing and vacuum drying;
step 2, treatment of a hydrophobic base film: soaking a hydrophobic basal membrane in isopropanol, then soaking in deionized water, standing and airing, soaking the hydrophobic basal membrane soaked in isopropanol and deionized water in a Tris-HCl buffer solution of dopamine, stirring at room temperature for reaction, washing with deionized water for a plurality of times, and airing for later use;
step 3, preparation of an MXene doped photothermal distillation membrane: dissolving the solid powder of the MXene doped composite photo-thermal material obtained in the step 1 in deionized water for ultrasonic dispersion, then combining the solid powder with the surface of the hydrophobic substrate film treated in the step 2, washing the surface of the film with deionized water, and then immersing the film into absolute ethyl alcohol to remove the redundant MXene doped composite photo-thermal material, thus obtaining the MXene doped photo-thermal distillation film.
4. The method for preparing the MXene doped photothermal distillation membrane according to claim 3, wherein in the step 1, the mass ratio of MXene to hydrophilic polymer is 1-200:10, the hydrophilic polymer is polydopamine, polyvinyl alcohol, polyethylene glycol, polyethyleneimine, graphene oxide, chitosan, sodium alginate, cellulose and a copolymer or a composition of the above substances, and the mass ratio of dopamine hydrochloride to MXene/hydrophilic polymer mixture is 1:1-5.
5. The method for preparing an MXene doped photothermal distillation membrane according to claim 3, wherein the time of ultrasonic dispersion in the step 1 is 0.5-2 h; stirring at room temperature for 0.5-2 h; the temperature of the water bath is 50-80 ℃; the stirring reaction time in the water bath is 1-24 h, and the stirring speed is 400-900 rpm; the centrifugation time is 10-20 min, and the rotating speed is 3000-5000 rpm; the washing is performed more than 3 times.
6. The method for preparing an MXene doped photothermal distillation membrane according to claim 3, wherein the concentration of Tris-HCl buffer solution in step 1 and step 2 is 50mmol/L, ph=8.5, and the concentration of Tris-HCl buffer solution of dopamine in step 2 is 0.2-2 g/L.
7. The method for preparing a MXene doped photothermal distillation membrane according to claim 3, wherein the hydrophobic substrate membrane in the step 2 is one of polytetrafluoroethylene, polyvinylidene fluoride and polypropylene.
8. The method for preparing an MXene doped photothermal distillation membrane according to claim 3, wherein the isopropanol soaking time in the step 2 is 1-2 h, the deionized water soaking time is 6-14 h, the stirring reaction time is 1-24 h, and the washing is more than 3 times.
9. The method for preparing a MXene doped photothermal distillation membrane according to claim 3, wherein the ultrasonic dispersion time in the step 3 is 1-6 h, and the loading amount of the MXene doped composite photothermal material on the surface of the treated hydrophobic substrate membrane is 0.1-5 mg/cm 2 The method for combining the surface of the hydrophobic substrate film treated in the step 2 is one of spraying, film scraping, vacuum filtration, dip coating or electrostatic spinning.
10. Use of an MXene doped photothermal distillation membrane according to claim 1 or 2 for the treatment of waste water containing inorganic salts and/or organic matter by membrane distillation.
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| CN117258546A (en) * | 2023-10-26 | 2023-12-22 | 山东大学 | Preparation method of MXene-based hydrogel composite photo-thermal membrane distillation membrane |
| CN117304563A (en) * | 2023-11-29 | 2023-12-29 | 中裕软管科技股份有限公司 | Multi-mode thermal management, antibacterial and antifouling polyurethane composite material for marine environment and preparation method and application thereof |
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| CN117258546A (en) * | 2023-10-26 | 2023-12-22 | 山东大学 | Preparation method of MXene-based hydrogel composite photo-thermal membrane distillation membrane |
| CN117258546B (en) * | 2023-10-26 | 2024-06-07 | 山东大学 | Preparation method of MXene-based hydrogel composite photo-thermal membrane distillation membrane |
| CN117304563A (en) * | 2023-11-29 | 2023-12-29 | 中裕软管科技股份有限公司 | Multi-mode thermal management, antibacterial and antifouling polyurethane composite material for marine environment and preparation method and application thereof |
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