CN115845629A - Preparation method and application of anti-pollution hydrogel composite membrane for membrane distillation - Google Patents
Preparation method and application of anti-pollution hydrogel composite membrane for membrane distillation Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
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Abstract
The invention provides a preparation method of an anti-pollution hydrogel composite membrane for membrane distillation, which comprises the following steps: carrying out oxygen plasma treatment on the supporting layer of the hydrophobic membrane to obtain a membrane product after plasma treatment; the hydrophobic membrane is selected from a polytetrafluoroethylene hydrophobic membrane or a polyvinylidene fluoride hydrophobic membrane; and (3) graft copolymerizing the hydrogel prepolymerization solution in the interior and on the surface of the supporting layer of the membrane product after plasma treatment to obtain the anti-pollution hydrogel composite membrane. The invention also provides application of the anti-pollution hydrogel composite membrane in membrane distillation. The hydrogel composite membrane has strong underwater oil stain resistance, can effectively prevent oil stains from blocking hydrophobic membrane holes due to underwater hydrophilic super-oleophobic property, has excellent capability of preventing a surfactant from damaging the membrane holes, also has a certain salt resistance effect, can effectively prolong the service life of the hydrophobic membrane, has universality, and has popularization and application prospects in the fields of seawater desalination, treatment of produced water of oil and gas fields, treatment of industrial wastewater and the like.
Description
Technical Field
The invention belongs to the technical field of membrane distillation wastewater treatment, and particularly relates to a preparation method of an anti-pollution hydrogel composite membrane for membrane distillation, and further relates to application of the anti-pollution hydrogel composite membrane for membrane distillation.
Background
In recent years, under the double pressure of water resource shortage and water pollution, the traditional high-salinity wastewater treatment mode mainly based on discharge is restricted by more and more policies, and the zero-liquid discharge scheme for exploring high-salinity wastewater is gradually receiving more global attention and is rapidly developing. Electrodialysis, forward osmosis and membrane distillation are techniques for achieving zero liquid discharge, further concentrating the wastewater after the reverse osmosis stage. The membrane distillation has high inlet water salinity limit value (> 200 g/L), has a theoretical 100% interception effect on various inorganic salts (such as chloride and calcium salts) in a solution, has low operation temperature (generally 40-80 ℃), can effectively utilize low-grade waste heat, and is considered to be an effective way for solving the problem of high-salt wastewater.
However, when a commercial hydrophobic membrane is used for treating high-salinity wastewater with coexisting organic and inorganic pollutants, the strong hydrophobic interaction between organic pollutants such as oil drops and the surface of the membrane makes the membrane easy to be blocked by the pollutants such as oil and the like; organic contaminants like surfactants can reduce the surface tension of the liquid greatly increasing the risk of membrane pore wetting; with increasing salt concentration, the saturation concentration may be exceeded, and precipitation of crystals in the liquid phase (in-phase nucleation) at or near the membrane surface (out-of-phase nucleation) leads to membrane fouling, the presence of which can seriously affect the stable operation of the membrane distillation system.
In order to solve the problems, the most direct and effective method is to modify the membrane material, and in recent years, a plurality of membrane modification methods including methods of layer-by-layer assembly, coating and the like are developed, but basically, the defects of poor stability, damage to the membrane structure and the like exist, and the problem of treatment of high-salinity wastewater with coexisting organic and inorganic pollutants cannot be effectively solved by modifying the traditional membrane.
Therefore, the technical problem to be solved is to provide a universal composite membrane product capable of pertinently treating high-salinity wastewater containing oil and surfactant and a preparation method thereof.
Disclosure of Invention
An object of the present invention is to provide an anti-pollution hydrogel composite membrane for membrane distillation capable of effectively treating high-salinity wastewater containing oil and a surfactant.
One of the purposes of the invention is to provide a preparation method of an anti-pollution hydrogel composite membrane for membrane distillation, which can effectively treat high-salinity wastewater containing oil and surfactant.
The technical scheme adopted by the invention for realizing one of the purposes is as follows: the preparation method of the anti-pollution hydrogel composite membrane for membrane distillation is provided, and comprises the following steps:
carrying out oxygen plasma treatment on the supporting layer of the hydrophobic membrane to obtain a membrane product after plasma treatment; the hydrophobic membrane is selected from a polytetrafluoroethylene hydrophobic membrane or a polyvinylidene fluoride hydrophobic membrane;
and grafting and copolymerizing the hydrogel prepolymerization solution on the surface of the supporting layer of the membrane product treated by the plasma to obtain the anti-pollution hydrogel composite membrane.
The general idea of the invention is as follows: a key component in membrane distillation systems is a hydrophobic membrane, which has gas-permeable, water-impermeable properties, providing a transport path for water vapor. According to the invention, the copolymerization hydrogel is grafted on the surface of the hydrophobic membrane to form the hydrogel composite membrane, and in the operation process of membrane distillation, the hydrogel hydrophilic layer contacts with the feed solution, so that the hydrogel composite membrane has the underwater super-oleophobic characteristic and can effectively prevent oil stains from being attached to the surface of the membrane; in addition, the hydrophilic and hydrophobic composite structure can also effectively prevent the damage of the surfactant to the hydrophobic membrane, and further, the polyion hydrogel has the Tangnan effect, so that the concentration of salt ions in the hydrogel is always lower than that of external salt solution, and inorganic pollutants such as sodium chloride crystals cannot appear in the gel, so that the membrane pollution is reduced, and the stable operation of a membrane distillation system is ensured.
In the invention, the commercial hydrophobic membrane (polytetrafluoroethylene hydrophobic membrane or polyvinylidene fluoride hydrophobic membrane) with the supporting layer arranged at the bottom is adopted, so that the supporting property can be provided for the thinner hydrophobic layer, the stable operation of membrane distillation is ensured, the structure and the property of the polytetrafluoroethylene cannot be changed in the preparation process by carrying out oxygen plasma treatment on the supporting layer and grafting hydrogel in the supporting layer and on the surface, and the damage of the surface treatment on the structure of the hydrophobic layer is effectively avoided.
Further, the hydrophobic membrane includes a hydrophobic layer and a support layer. The hydrophobic layers of the polytetrafluoroethylene hydrophobic membrane and the polyvinylidene fluoride hydrophobic membrane are respectively polytetrafluoroethylene and polyvinylidene fluoride, and the support layer is selected from polypropylene or polyethylene terephthalate. The thickness of the hydrophobic layer is 5-15 μm, and the thickness of the support layer is 100-130 μm.
In some preferred embodiments, the thickness of the hydrophobic layer of the polytetrafluoroethylene hydrophobic membrane is 10 μm, the thickness of the support layer is 120 μm, and the pore diameter of the polytetrafluoroethylene hydrophobic membrane is 100nm and the diameter is 47nm.
In some preferred embodiments, the thickness of the hydrophobic layer of the polyvinylidene fluoride hydrophobic membrane is 10 μm, the thickness of the support layer is 110 μm, and the pore diameter of the polytetrafluoroethylene hydrophobic membrane is 220nm.
Furthermore, the power of the oxygen plasma treatment is 18-250W, and the time is 1-10 min. The grafting rate of the hydrogel on the surface of the supporting layer can be improved by adjusting the power and the treatment time of the oxygen plasma.
In the present invention, the method of graft-copolymerizing the hydrogel prepolymerization solution on the surface of the treated membrane product may be carried out by thermal polymerization or photo polymerization.
In the thermal polymerization method, the ratio of the amounts of the monomer to the crosslinking agent in the hydrogel prepolymer solution is 50 to 1000, preferably 50. The hydrogel layer of the invention needs to be applied to membrane distillation for treating high-salinity wastewater, which has higher requirements on the mechanical strength and the swelling performance of the hydrogel layer, and the swelling phenomenon of the hydrogel layer when contacting the high-salinity wastewater can be inhibited by controlling the proportion of the monomers, so that the hydrogel layer has higher mechanical strength, and the membrane distillation system can run stably for a long time.
Preferably, the monomer is selected from one or more of sodium 2-methyl-2-acrylamido propyl sulfonate, sodium acrylate, acrylamide, [2- (methacrylamidooxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, and sodium 2-acrylamido-2-methyl-1-propanesulfonate, and the concentration of the monomer is 1 to 3mol/L;
preferably, the cross-linking agent is N, N' -methylene-bisacrylamide with the concentration of 1-60 mmol/L;
the hydrogel pre-polymerization liquid also comprises a catalyst, wherein the catalyst is tetramethylethylenediamine, and the volume concentration of the catalyst is 0.1vol%.
Further, the method of graft copolymerization comprises: and (3) manufacturing a mold on the surface of the supporting layer of the membrane product after the plasma treatment, uniformly mixing the hydrogel pre-polymerization liquid and the initiator, inverting the mixture in the mold, covering a shaping plate on the surface of the mold, and reacting under a vacuum condition to obtain the anti-pollution hydrogel composite membrane.
Preferably, the initiator is ammonium persulfate, and the concentration of the initiator is 3 to 6mmol/L.
Preferably, the vacuum degree under the vacuum condition is 0.05-0.08 Mpa; the reaction temperature under the vacuum condition is 30-60 ℃.
In the above graft copolymerization method, plasma-activating a polypropylene support layer of commercial hydrophobic membrane polytetrafluoroethylene, extracting hydrogen from one functional group of a substrate side chain (i.e., COOH and C-oh.) by sulfate anion radical initiation reaction in a thermal initiator to form a corresponding radical, and then the generated radical initiates graft copolymerization of hydrogel, belonging to thermal polymerization in hydrogel preparation and not requiring a hydrophilic high molecular compound to be a ligament.
In the graft copolymerization by the photopolymerization method, the ratio of the amounts of the monomer and the crosslinking agent in the hydrogel prepolymer solution is 50 to 1000, preferably 50.
The monomer is selected from one or more of 2-methyl-2-acrylamide propyl sodium sulfonate, sodium acrylate, acrylamide, [2- (methacrylamide acyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and 2-acrylamide-2-methyl-1-propyl sodium sulfonate, and the concentration of the monomer is 1-3 mol/L; the cross-linking agent is N, N' -methylene-bisacrylamide, and the concentration of the cross-linking agent is 1-60 mmol/L.
Further, the method of graft copolymerization comprises: and (2) immersing the surface of the supporting layer of the membrane product after the plasma treatment into a silane coupling agent solution for pretreatment, manufacturing a mould on the surface of the supporting layer of the membrane product after the pretreatment, inverting the hydrogel pre-polymerization solution in the mould, and carrying out polymerization reaction under the protection of nitrogen in an ultraviolet light chamber to obtain the anti-pollution hydrogel composite membrane.
Preferably, the photoinitiator is selected from 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl]-1-acetone or alpha-ketoglutaric acid, at a concentration of 1 to 30mmol/L. The ultraviolet wavelength of the polymerization reaction is 365nm, and the ultraviolet intensity is 4mW cm -2 The time of the polymerization reaction is 4 to 8 hours. More preferably, the polymerization time is 6h.
Further, the preparation method of the silane coupling agent solution comprises the following steps: 3- (methacryloyloxy) propyl trimethoxy silane and glacial acetic acid are added into deionized water according to the adding amount of 20g/L and 0.015 vol% respectively, and are mixed for 4 hours to obtain a silane coupling agent solution.
In the above graft copolymerization method, a high-density functional group is generated by plasma treatment of the side of the polyethylene terephthalate support layer, a silane coupling agent is used as a bridge, and then the hydrogel is polymerized by a photo process.
The two methods can prepare the anti-pollution hydrogel composite membrane for membrane distillation, the structure of which comprises the polytetrafluoroethylene hydrophobic layer and the hydrogel layers embedded in and on the supporting layer. Further, in the present invention, the thickness of the hydrogel can be controlled to realize the adjustment of heat and mass transfer in the membrane distillation. In the present invention, the thickness of the hydrogel layer is 50 μm to 5mm. Preferably, the hydrogel layer has a thickness of 50 to 100 μm.
The second technical scheme adopted for achieving the purpose of the invention is as follows: there is provided a use of an anti-contamination hydrogel composite membrane for membrane distillation prepared by the preparation method according to one of the objects of the present invention, comprising: and placing the anti-pollution hydrogel composite membrane in system membrane distillation in a mode that the hydrogel side is close to the hot end and the polytetrafluoroethylene side is close to the cold end.
When the hydrogel composite membrane prepared by the invention is used, the hydrogel side is required to be kept in contact with hot end wastewater, and the oil stain is prevented from contacting with the hydrophobic membrane to block the hydrophobic hole by virtue of the blocking effect of the hydrogel layer on the oil stain; simultaneously, the structure of aquogel complex film can also hinder surfactant agent to lead to the fact the destruction to hydrophobic membrane, if the aquogel layer then can't realize above-mentioned function towards the cold junction. In use, the evaporation interface of the hydrogel composite membrane of the invention is located at the interface of the hydrogel and the hydrophobic membrane.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the anti-pollution hydrogel composite membrane for membrane distillation provided by the invention comprises the step of graft copolymerizing a hydrogel prepolymerization solution on the surface of the support layer of the membrane product treated by plasma to obtain the anti-pollution hydrogel composite membrane. By means of the three-dimensional network structure of the hydrogel, the concentration of the monomer and the cross-linking agent can be adjusted to intelligently adjust the inner pores of the hydrogel to block macromolecular substances. The preparation method provided by the invention has the advantages of simple process, easily obtained materials and low cost, and has the potential of being applied to large-scale industrial production.
(2) The anti-pollution hydrogel composite membrane for membrane distillation, which is prepared by the invention, has strong underwater oil stain resistance, and compared with commercial polytetrafluoroethylene, polyvinylidene fluoride and polypropylene hydrophobic membranes, the composite membrane has the underwater hydrophilic and oleophobic properties and can prevent oil stains from blocking the pores of the hydrophobic membrane. In addition, the hydrogel composite membrane has excellent capability of preventing the destruction of the membrane pores by the surfactant. Commercial hydrophobic membranes are highly susceptible to permanent failure by wetting the membrane pores in the presence of surfactants and salt ions, and the hydrogel layer of the composite membrane prevents the destruction of the membrane pores by low surface tension materials like surfactants. Furthermore, the hydrogel composite membrane also has a certain salt-resistant effect, and the concentration of salt ions in the hydrogel composite membrane is always lower than that of an external solution based on the Thangnan effect.
(3) The anti-pollution hydrogel composite membrane for membrane distillation, which is prepared by the invention, can be applied to other membrane separation technologies such as oil-water separation and the like by compounding hydrogel and nano fibers, so that the anti-pollution hydrogel composite membrane has strong universality, can also be applied to a plurality of fields such as seawater desalination, oil-gas field produced water treatment, industrial wastewater treatment and the like, and has wide popularization and application prospects.
Drawings
FIG. 1 is a schematic diagram illustrating the operation principle of an anti-pollution hydrogel composite membrane for membrane distillation in a membrane distillation system according to the present invention;
FIG. 2 is a flow chart of a method for preparing a hydrogel composite membrane according to example 1 of the present invention;
FIG. 3 is a flow chart of a method for preparing a hydrogel composite membrane according to example 5 of the present invention;
FIG. 4 is a scanning electron micrograph of a hydrogel composite membrane provided in example 1 of the present invention;
fig. 5 is a graph showing the surface hydrophilic contact angle and the underwater oil contact angle of the hydrogel composite membrane provided in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
The main raw materials and parameters of examples 1 to 6 of the present invention are shown in table 1 below.
TABLE 1
In the above table, the first and second sheets,
the hydrophobic membranes of polytetrafluoroethylene used in examples 1-4 were those of PTFE available from Sterlitech, USA, with a PTFE thickness of about 10 μm, a support layer thickness of about 120 μm, a polypropylene layer as the support layer, a pore size of 100nm and a diameter of 47mm.
Examples 5 and 6 used polyvinylidene fluoride hydrophobic membranes polytetrafluoroethylene hydrophobic membranes provided by Deffx New materials science and technology, inc., hainin, china, having a PTFE thickness of 10 μm, a support layer thickness of 110 μm, a pore diameter of 220 μm and a diameter of 50mm.
The PLASMA cleaner was supplied by HARRICK PLASMA, USA, and is model number PDC-32G-2.
Example 1
Step 1: 10mL of deionized water, 1.8808g of sodium acrylate, 0.061668gN, N' -methylene bisacrylamide and 10 uL of tetramethylethylenediamine are sequentially added into a container, dissolved uniformly by ultrasonic, and dissolved oxygen is removed by bubbling nitrogen for 10min.
Step 2: immersing the polytetrafluoroethylene flat membrane provided with the polypropylene supporting layer in an ethanol solution, treating for 10min by adopting ultrasonic waves, and drying the membrane for 24h in a nitrogen environment.
And step 3: a circular mold having a diameter of 38mm and a thickness of 100 μm was formed on the polypropylene-side surface of the polytetrafluoroethylene hydrophobic film, and oxygen plasma treatment at a power of 18W was performed for 4min to generate high-density active functional groups in the polypropylene fiber by controlling plasma discharge.
And 4, step 4: to the solution of the above step 1, 40. Mu.L of ammonium persulfate (228 mg/L) was added to obtain a hydrogel prepolymerized solution.
And 5: and (3) pouring the hydrogel pre-polymerization liquid obtained in the step (4) on the surface of the polypropylene treated by the oxygen plasma under the nitrogen protection environment, adding a layer of glass upper cover plate for shaping, then adopting a vacuum negative pressure pump for loading, controlling the vacuum degree to be 0.05-0.08 MPa, and reacting for 4 hours under the nitrogen protection to form the hydrogel composite membrane.
Example 2
Step 1: 10mL of deionized water, 2.13g of acrylamide, 0.0046251gN, N' -methylene bisacrylamide and 10 mu L of tetramethylethylenediamine are sequentially added into a container, dissolved uniformly by ultrasonic waves and dissolved oxygen is removed by bubbling nitrogen for 10min.
Step 2: immersing the polytetrafluoroethylene flat membrane provided with the polypropylene supporting layer in an ethanol solution, treating for 10min by adopting ultrasonic waves, and drying the membrane for 24h in a nitrogen environment.
And step 3: a circular mold having a diameter of 38mm and a thickness of 100 μm was formed on the polypropylene-side surface of the polytetrafluoroethylene hydrophobic film, and oxygen plasma treatment at a power of 18W was performed for 4min to generate high-density active functional groups in the polypropylene fiber by controlling plasma discharge.
And 4, step 4: 60. Mu.L of ammonium persulfate (228 mg/L) was added to the solution of the above step 1 to obtain a hydrogel prepolymerized solution.
And 5: and (3) pouring the hydrogel pre-polymerization liquid obtained in the step (4) on the surface of the polypropylene treated by the oxygen plasma under the nitrogen protection environment, adding a layer of glass upper cover plate for shaping, then adopting a vacuum negative pressure pump for loading, controlling the vacuum degree to be 0.05-0.08 MPa, and reacting for 3 hours under the nitrogen protection to form the hydrogel composite membrane.
Example 3
Step 1: 7.7077mL of deionized water, 4.5846g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt solution (50 wt% aqueous solution), 0.030834g of N, N' -methylenebisacrylamide and 10. Mu.L of tetramethylethylenediamine were sequentially added to a vessel, dissolved by ultrasonic waves uniformly, and dissolved oxygen was removed by bubbling nitrogen gas for 10min.
Step 2: immersing the polytetrafluoroethylene flat membrane provided with the polypropylene supporting layer in an ethanol solution, treating for 10min by adopting ultrasonic waves, and drying the membrane for 24h in a nitrogen environment.
And step 3: a circular mold having a diameter of 38mm and a thickness of 100 μm was formed on the polypropylene-side surface of the polytetrafluoroethylene hydrophobic film, and oxygen plasma treatment was performed at a power of 250W for 1min to generate high-density reactive functional groups in the polypropylene fiber by controlling plasma discharge.
And 4, step 4: to the solution of the above step 1, 50. Mu.L of ammonium persulfate (228 mg/L) was added to obtain a hydrogel prepolymerized solution.
And 5: and (3) pouring the hydrogel pre-polymerization liquid obtained in the step (4) on the surface of the polypropylene treated by the oxygen plasma under the nitrogen protection environment, adding a layer of glass upper cover plate for shaping, then adopting a vacuum negative pressure pump for loading, controlling the vacuum degree to be 0.05-0.08 MPa, and reacting for 3.5 hours under the nitrogen protection to form the hydrogel composite membrane.
Example 4
Step 1: to 150ml of deionized water, 3g of 3- (methacryloyloxy) propyltrimethoxysilane and 22. Mu.L of glacial acetic acid were added and the mixture was stirred at room temperature for 4 hours and mixed uniformly for further use.
Step 2: commercial polytetrafluoroethylene hydrophobic membranes were rinsed with ethanol for 10min and placed in a vacuum oven prior to use. The polypropylene support layer on the bottom of the hydrophobic polytetrafluoroethylene membrane was treated with oxygen plasma at 250w power for 1 minute to further increase the surface roughness. Meanwhile, the surface of the polyethylene terephthalate has abundant hydroxyl groups.
And step 3: and immersing the polypropylene surface treated by the plasma into a silane coupling agent solution for 12 hours, hydrolyzing alkoxy at one end into silanol in a water environment, and condensing with hydroxyl on the surface of a target to form a siloxane bond so as to form strong bonding between a target substrate and a bridge molecule.
And 4, step 4: 7.7077mL of deionized water, 4.5846g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt solution (50 wt% aqueous solution), 0.030834g of N, N' -methylenebisacrylamide, 0.022425g of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone were added to a vessel, dissolved uniformly by sonication and bubbling with nitrogen for 10min to remove dissolved oxygen.
And 5: and (3) manufacturing a mold on the surface of one side of the support layer of the membrane product treated in the step (3), inverting the hydrogel pre-polymerization liquid, covering a glass plate for qualitative determination, irradiating for 4h in a 365nm ultraviolet lamp polymerization chamber, and allowing vinyl at the other end of the 3- (methacryloyloxy) propyl trimethoxy silane to participate in the polymerization of the hydrogel precursor to form a covalent bond, thereby finally obtaining the hydrogel composite membrane.
Example 5
Step 1: to 150ml of deionized water, 3g of 3- (methacryloyloxy) propyltrimethoxysilane and 22. Mu.L of glacial acetic acid were added and the mixture was stirred at room temperature for 4 hours and mixed uniformly for further use.
Step 2: commercial polyvinylidene fluoride hydrophobic membranes were rinsed with ethanol for 10min and placed in a vacuum oven prior to use. The polyethylene terephthalate support layer on the bottom of the polyvinylidene fluoride hydrophobic membrane was treated with oxygen plasma at 18w power for 10 minutes to further increase the surface roughness. Meanwhile, the surface of the polyethylene terephthalate has abundant hydroxyl groups.
And step 3: and immersing the surface of the polyethylene glycol terephthalate after the plasma treatment in a silane coupling agent solution for 12h, hydrolyzing alkoxy at one end in a water environment to form silanol groups, and condensing with hydroxyl on the surface of a target to form siloxane bonds, so that strong bonding is formed between the target substrate and bridge molecules.
And 4, step 4: 10mL of deionized water, 2.8212g of sodium acrylate, 0.0046251gN, N' -methylene bisacrylamide and 10 mu L of tetramethylethylenediamine are sequentially added into a container, dissolved uniformly by ultrasonic waves, and dissolved oxygen is removed by bubbling nitrogen for 10min.
And 5: to the solution of the above step 4, 50. Mu.L of ammonium persulfate (228 mg/L) was added to obtain a hydrogel prepolymerization solution.
Step 6: and (3) pouring the hydrogel pre-polymerization liquid obtained in the step (4) on the surface of the polyethylene terephthalate treated by the oxygen plasma in a nitrogen protection environment, adding a layer of glass upper cover plate for shaping, then adopting a vacuum negative pressure pump for loading, controlling the vacuum degree to be 0.05-0.08 Mpa, and reacting for 3.5 hours under the protection of nitrogen to form the hydrogel composite membrane.
Example 6
Step 1: to 150ml of deionized water, 3g of 3- (methacryloyloxy) propyltrimethoxysilane and 22. Mu.L of glacial acetic acid were added and the mixture was stirred at room temperature for 4 hours and mixed uniformly for further use.
Step 2: the commercial polyvinylidene fluoride hydrophobic membrane was washed with ethanol for 10min and placed in a vacuum oven prior to use. The polyethylene terephthalate support layer on the bottom of the polyvinylidene fluoride hydrophobic membrane was treated with oxygen plasma at 18w power for 10 minutes to further increase the surface roughness. Meanwhile, the surface of the polyethylene terephthalate has abundant hydroxyl groups.
And step 3: and (3) immersing the surface of the polyethylene glycol terephthalate after the plasma treatment in a silane coupling agent solution for 12 hours, hydrolyzing alkoxy at one end in a water environment to form silanol group, and condensing with hydroxyl on the surface of a target to form a siloxane bond so as to form strong bonding between the target substrate and a bridge molecule.
And 4, step 4: 10mL of deionized water, 1.4216g of acrylamide, 0.030834g of N, N' -methylene bisacrylamide and 0.00292g of alpha-ketoglutaric acid are sequentially added into a container, dissolved uniformly by ultrasonic, and dissolved oxygen is removed by bubbling nitrogen for 10min.
And 5: and (3) manufacturing a mold on the surface of one side of the supporting layer of the membrane product treated in the step (3), inverting the hydrogel pre-polymerization liquid, covering a glass plate for qualitative use, irradiating for 8h in a 365nm ultraviolet lamp polymerization chamber, and allowing vinyl at the other end of the 3- (methacryloyloxy) propyl trimethoxy silane to participate in polymerization of a hydrogel precursor to form a covalent bond to finally obtain the hydrogel composite membrane.
Comparative example 1
The same hydrophobic polytetrafluoroethylene membrane (PTFE hydrophobic membrane supplied by Sterlitech corporation, usa) as in examples 1 to 4 was used.
Comparative example 2
The same polyvinylidene fluoride hydrophobic membrane (polyvinylidene fluoride hydrophobic membrane provided by delofilter materials science and technology ltd, haining, china) as in examples 5 and 6 was used.
Performance testing
(first) hydrophilicity and oleophobicity test
FIG. 4 is a scanning electron microscope image of a hydrogel composite membrane finally obtained in example 1 of the present invention; fig. 5 is a graph showing the surface hydrophilic contact angle and the underwater oil contact angle of the hydrogel composite membrane provided in example 1 of the present invention.
As can be seen from FIG. 5, the water contact angle of the hydrogel composite membrane prepared by the invention is less than 5 degrees, which indicates that the hydrogel composite membrane has good hydrophilicity, the dynamic contact angle of underwater oil is 180 degrees, and the modified membrane shows ultralow adhesion with oil drops and excellent superoleophobic property in the dynamic process that the oil drops gradually contact with and leave the membrane surface.
(II) wastewater treatment ability test
Configuring a wastewater sample A and a wastewater sample B, wherein: the wastewater sample A is 0.1mM sodium dodecyl sulfate and 1000ppm mineral oil which are mixed in 3.5wt% NaCl solution to obtain O/W wastewater; wastewater sample B was a wastewater containing 2000ppm mineral oil in a 3.5wt.% NaCl solution.
The flux and salt rejection of the hydrogel composite membranes prepared in examples 1-6 and the membranes in comparative examples 1 and 2 were evaluated by the change in the quality and conductivity of permeate side water at 60 ℃ in the hot side and 20 ℃ in the cold side using a direct contact membrane distillation test system, and the test results are shown in table 2 below.
Table 2:
as can be seen from the above table,
when the hot-end wastewater is O/W, the normalized steam flux of the original polytetrafluoroethylene hydrophobic membrane (comparative example 1) is remarkably increased within 45min of operation time, the salt rejection rate is greatly reduced, and the polytetrafluoroethylene hydrophobic membrane is seriously wetted, so that the hydrogel composite membrane (examples 1-4) can have 100 percent of salt rejection and relatively stable steam flux within 10 h. When the hot end wastewater was 2000ppm mineral oil, the steam flux of the original polyvinylidene fluoride hydrophobic membrane (comparative example 2) dropped rapidly shortly after the start of the experiment, indicating severe contamination of the membrane with mineral oil. In contrast, the hydrogel composite membranes prepared in examples 5-6 were able to maintain relatively stable vapor flux and perfect salt rejection over 10 hours, indicating good fouling resistance.
In summary, according to the preparation method of the anti-pollution hydrogel composite membrane for membrane distillation provided by the invention, the hydrogel layers are constructed in the middle and on the surface of the support layer of the hydrophobic membrane, and the successfully prepared hydrogel composite membrane shows excellent performance in treatment of high-salinity wastewater containing oil and surfactant.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of an anti-pollution hydrogel composite membrane for membrane distillation comprises the following steps:
carrying out oxygen plasma treatment on the supporting layer of the hydrophobic membrane to obtain a membrane product after plasma treatment; the hydrophobic membrane is selected from a polytetrafluoroethylene hydrophobic membrane or a polyvinylidene fluoride hydrophobic membrane;
and grafting and copolymerizing the hydrogel prepolymerization solution on the surface of the supporting layer of the membrane product treated by the plasma to obtain the anti-pollution hydrogel composite membrane.
2. The production method according to claim 1, wherein the hydrophobic membrane includes a hydrophobic layer and a support layer; the support layer is selected from polypropylene or polyethylene terephthalate.
3. The method of claim 1, wherein the oxygen plasma treatment is performed at a power of 18 to 250W for a time of 1 to 10min.
4. The production method according to claim 1, wherein the hydrogel prepolymerized liquid has a ratio of the amount of the monomer to the amount of the crosslinking agent of 50 to 1000; the monomer is selected from one or more of 2-methyl-2-acrylamide propyl sodium sulfonate, sodium acrylate, acrylamide, [2- (methacrylamide acyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and 2-acrylamide-2-methyl-1-propyl sodium sulfonate; the cross-linking agent is N, N' -methylene bisacrylamide.
5. The method of claim 4, wherein the hydrogel pre-polymerization solution further comprises a catalyst; the catalyst is tetramethylethylenediamine, and the volume concentration of the catalyst is 0.1vol%.
6. The production method according to claim 5, wherein the graft copolymerization method comprises: and (3) manufacturing a mold on the surface of the supporting layer of the membrane product after the plasma treatment, uniformly mixing the hydrogel pre-polymerization liquid and the initiator, inverting the mixture in the mold, covering a shaping plate on the surface of the mold, and reacting under a vacuum condition to obtain the anti-pollution hydrogel composite membrane.
7. The preparation method according to claim 6, wherein the initiator is ammonium persulfate, and the concentration of the initiator is 3-6 mmol/L; the vacuum degree under the vacuum condition is 0.05-0.08 Mpa; the reaction temperature under the vacuum condition is 30-60 ℃.
8. The production method according to claim 4, wherein the graft copolymerization method comprises: and (3) immersing the surface of the supporting layer of the membrane product subjected to plasma treatment into a silane coupling agent solution for pretreatment, manufacturing a mold on the surface of the supporting layer of the membrane product subjected to pretreatment, inverting the hydrogel prepolymerization solution in the mold, and carrying out polymerization reaction under the protection of nitrogen in an ultraviolet light chamber to obtain the anti-pollution hydrogel composite membrane.
9. The method of claim 8, wherein the photoinitiator is selected from the group consisting of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and α -ketoglutaric acid at a concentration of 1 to 30mmol/L; the ultraviolet wavelength of the polymerization reaction is 365nm, and the polymerization reaction time is 4-8 h.
10. Use of an anti-fouling hydrogel composite membrane for membrane distillation prepared by the preparation method according to any one of claims 1 to 9, wherein the anti-fouling hydrogel composite membrane is placed in a membrane distillation system with the hydrogel side close to the hot end and the hydrophobic side close to the cold end.
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