CN110756065A - Hydrotalcite-like nanosheet modified separation membrane, and preparation method and application thereof - Google Patents
Hydrotalcite-like nanosheet modified separation membrane, and preparation method and application thereof Download PDFInfo
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Abstract
The preparation method comprises the step of coating and converting a casting solution, wherein the casting solution contains the hydrotalcite-like nanosheets. The mutual synergistic action between the hydrotalcite-like compound and the hydrophilic polymer ensures that the hydrophilic polymer is stabilized in the membrane and cannot be separated out in the phase inversion process, thereby reducing the using amount of the hydrophilic polymer and reducing the pollution to the water environment. In addition, the preparation process of the porous separation membrane is simple in process and low in cost, and has very important significance for realizing application. Under the same test conditions, the separation membrane prepared by the method has the characteristics of high flux, good hydrophilicity and high mechanical strength.
Description
Technical Field
The invention belongs to the field of membrane separation, and particularly relates to a membrane material and a preparation method thereof.
Background
Membrane separation is a physical process in which no phase change occurs. Techniques for achieving separation by using a polymeric membrane as the selective separation layer to allow certain components to permeate while retaining other components in the mixture. At present, the method is applied to the fields of seawater desalination, wastewater treatment, food and medicine, energy and the like. The separation membrane is the core of the membrane separation process, and the quality of the membrane performance determines the operation cost of the membrane separation process and whether the membrane separation process can be popularized on a large scale. Therefore, separation membranes with high flux, high rejection, and contamination resistance are desired.
Currently, most commercial separation membranes are prepared by phase inversion of polymers, which is usually performed by dissolving polymers in organic solvents to obtain a casting solution with a certain concentration, coating the casting solution into a liquid film, and converting the liquid film in a non-solvent (usually water) to obtain a porous separation membrane. In order to improve the flux of separation and contamination resistance, a hydrophilic polymer is generally used as a membrane material for preparing a porous separation membrane. However, since the hydrophilic polymer is less stable in water, it is easily precipitated from the porous membrane into water during phase inversion, which causes loss of the amount of the hydrophilic polymer; meanwhile, the precipitated hydrophilic polymer can cause serious pollution to the water environment.
The nano material as a modified material promotes the physical and chemical properties of the porous separation membrane. In the prior art, the conventional method is to directly blend and modify a porous separation membrane with a nano material to improve the flux and the hydrophilicity of the membrane, and the core of the function is the nano material. For example: CN 105056768A reports a technical scheme of modifying a support layer of a forward osmosis composite membrane by using spherical hydrotalcite-like nano-particles and co-particles, and the support layer is a hydrotalcite-like composite porous support layer membrane which has more excellent porosity, hydrophilicity and flux. Hydrotalcite-like compounds are Layered metal hydroxides (LDHs) which have high specific surface area, good hydrophilicity and good catalytic performance; meanwhile, the material also has heat resistance and radiation resistance, and is a good two-dimensional inorganic nano material. The stripped hydrotalcite-like nanosheets are commonly used in the fields of catalysis, supercapacitors, light-emitting devices, flame retardants and the like.
Disclosure of Invention
The invention aims to provide a porous separation membrane which reduces the use amount of hydrophilic polymers, is environment-friendly and has better performance.
Therefore, the invention firstly provides a preparation method of the hydrotalcite-like nano-sheet modified separation membrane, which comprises the step of coating and converting a casting solution, wherein the casting solution contains the hydrotalcite-like nano-sheets.
Unlike the prior art method of blending hydrotalcite-like compounds to modify porous separation membranes, the present invention does not rely on the proven effects of hydrotalcite-like compounds. Tests prove that the hydrotalcite-like compound is more suitable to be defined as a fixing material to play a role. The mutual synergistic effect between the hydrophilic polymer and the hydrophilic polymer ensures that the hydrophilic polymer is stabilized in the membrane and cannot be separated out in the phase inversion process, thereby reducing the using amount of the hydrophilic polymer and reducing the pollution to the water body environment. In addition, the preparation process of the porous separation membrane is simple in process and low in cost, and has very important significance for realizing application. Under the same test conditions, the porous separation membrane prepared by the invention has the characteristics of high flux, good hydrophilicity and high mechanical strength. Accordingly, it is another aspect of the present invention to provide a hydrotalcite-like nanosheet-modified separation membrane prepared by the above-described method. Based on the application of the porous separation membrane of the present invention as described above, the present invention further provides a composite membrane comprising: the porous separation membrane of the present invention and the composite membrane obtained by performing interfacial polymerization on the surface of the porous separation membrane are provided.
Drawings
The invention is illustrated in figure 5:
FIG. 1 shows the turbidity of the NMP solvent and hydrotalcite-like stripping solution;
FIG. 2 is turbidity of the gel bath;
FIG. 3 is a UV-Vis spectroscopy spectrum of a gel bath;
FIG. 4 is a pure water flux of a porous separation membrane;
FIG. 5 is water flux and reverse salt flux of composite membranes
Detailed Description
The core technical scheme of the invention is to provide a method for preparing a porous separation membrane with reduced amount and environmental protection, and the main technical purposes comprise preparation of the porous separation membrane, reduction of the using amount of a hydrophilic polymer and improvement of membrane performance. In an improved technical scheme about the preparation method, a step of coating and converting a casting solution is included, and the core technology is characterized in that the casting solution containing hydrotalcite-like nano-sheets is used. More specifically, the content of the hydrotalcite-like nanosheets in the casting solution is 0.1-1 wt%. Preferably, the content of the hydrotalcite-like nano-sheets is 0.3-0.5 wt%.
In a specific embodiment, a hydrotalcite-like compound stripping solution is added into the casting solution to obtain a casting solution containing hydrotalcite-like compound nanosheets; the hydrotalcite-like compound is selected from hydrotalcite-like compounds with nitrate radical, acetate radical, lactate radical and stearate radical intercalation; the organic solvent is selected from one or a mixture of more of formamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone. Nitrate intercalated magnesium aluminium hydrotalcite is preferred.
The above hydrotalcite-like exfoliating solution can be prepared by referring to the prior art in the field, and as a specific embodiment, the hydrotalcite-like exfoliating solution is prepared by mechanically exfoliating hydrotalcite-like in an organic solvent. In order to obtain the technical effect required by the invention, the concentration of the hydrotalcite-like nanosheet in the obtained hydrotalcite-like stripping liquid is ensured to be 1-10 g L-1. The hydrotalcite-like stripping liquid plays a role in fixing a hydrophilic polymer material, and the selection of the concentration of the hydrotalcite-like stripping liquid influences important parameters such as the pore size, the pore distribution, the porosity and the like of the prepared porous separation membrane; the examples of the invention fully demonstrate the 1,2,4 and 6g L tested-1The hydrotalcite-like compound stripping liquid under the condition of equal concentration can meet the technical requirements of the invention and realize corresponding technical effects.
On the other hand, in the solution of the present invention, the casting solution further contains a hydrophilic polymer, but the polymer in the casting solution is much less limited. It is easily understood based on the core technical solution of the present invention that, supported by the prior art conditions, polymers capable of constructing porous separation membranes can be used in the present invention, and the polymers are selected from but not limited to one or a mixture of more of polysulfone, polyethersulfone, polyphenylenesulfone, polyvinylidene fluoride, polybenzimidazole, sulfonated polysulfone, sulfonated polyethersulfone, and sulfonated polyetheretherketone; sulfonated polysulfone, sulfonated polyethersulfone, and sulfonated polyetheretherketone are preferred.
On the other hand, the hydrotalcite-like nano-scale stripping solution used in the present invention is also well reported in the prior art, and can be described according to the existing records in the field of nano-materials (appl.clay sci.55(2012) 18-26), and its general formula is: [ M ] A(II) 1-xM(III) x(OH)2]x+[(An-)x/n·mH2O]x-Wherein M is(II)May be Mg2+、Cu2+、Co2+、Zn2+、Ni2+Any divalent metal ion; m(III)May be Al3+、Ti3+、Fe3+、Cr3+And the like, any trivalent metal ion; a. then-Can be NO3 –、SO4 2–、PO4 3–One or more of inorganic, organic or complex anions such as stearate, lactate, lauryl sulfate and fatty acid radical. The hydrotalcite-like stripping solution capable of stripping is formed by preferably selecting metal cations and interlayer anions suitable for stripping, wherein the interlayer anions are preferably nitrate radical, acetate radical, lactate radical and stearate radical intercalated hydrotalcite-like.
Finally, in the preparation of the casting solution, the solvent used is an organic solvent selected from dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or tetrahydrofuran. It is to be understood that this is by way of illustration and not of limitation.
In a more specific embodiment, the preparation method of the hydrotalcite-like nanosheet modified separation membrane comprises the following steps:
the first step is as follows: and (3) synthesizing hydrotalcite-like particles. The hydrotalcite-like particles can be synthesized by the traditional coprecipitation method, hydrothermal method, solvothermal method, urea method and the like. The synthesized hydrotalcite-like particles are washed with deionized water to pH 7, and then thoroughly washed and dried with an organic solvent such as acetone, methanol, or ethanol for use.
The second step is that: preparing hydrotalcite-like compound stripping liquid and casting liquid. And dispersing hydrotalcite-like compound with certain mass in an organic solvent, stirring, and carrying out ultrasonic treatment for a period of time to obtain hydrotalcite-like compound stripping liquid with certain concentration. And adding a polymer into the stripping solution, and stirring and defoaming to obtain the hydrotalcite-like nanosheet/polymer membrane casting solution.
The third step: and (3) coating the casting solution on a smooth glass plate or spinning in a spinning machine, then soaking in water for 12 hours, and performing phase inversion to obtain the flat plate type or hollow fiber porous separation membrane.
Further, the invention provides a porous separation membrane prepared according to any of the above technical schemes; and carrying out reaction on the surface of the porous separation membrane layer to obtain the composite membrane.
Generally, a composite membrane includes a porous separation membrane layer and a polyamide active layer, and the polyamide active layer is obtained by interfacial polymerization at the surface of the porous separation membrane. The selection of the polyamide active layer in the specific embodiments, based on the description above, can be carried out by a person skilled in the art on the basis of the description of such composite films in the prior art. The following will further explain the preparation process of the composite film.
In the present invention, the preparation of the composite membrane includes the steps of sequentially immersing the dense side of the porous separation membrane in an amine solution and an acid chloride solution, and then performing a thermal polymerization process. In a specific embodiment, the mass concentration of the amine solution is 1-5 wt%, the solvent is water, and the amine is selected from, but not limited to, m-phenylenediamine, p-phenylenediamine and piperazine; the mass concentration of the acyl chloride solution is 0.05-0.5%, and the solvent is selected from but not limited to n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, Isopar E or Isopar G.
A further specific method of preparing the composite membrane can be described as: immersing the compact side of the porous separation membrane into 1-5 wt% of amine water solution for 1-3 min, and removing redundant solution on the surface after taking out; then putting the porous support layer soaked by the amine into 0.05-0.5 wt% of acyl chloride solution for 1-3 min; taking out, carrying out heat treatment for 1-3 min, then respectively washing with 200ppm of sodium hypochlorite aqueous solution and 1000ppm of sodium bisulfite aqueous solution, and finally carrying out heat treatment for 2min to obtain the composite film. Wherein the temperature of the heat treatment is determined according to the specific selected amine substance and acid chloride substance, and the prior art can be referred to.
In a more specific embodiment, the method for preparing the composite membrane comprises the following steps:
immersing the dense side of the porous separation membrane into 1-5 wt% of amine water solution for 2min, taking out, and blowing off redundant solution droplets on the surface by using an air knife; then placing the compact side into 0.05-0.5 wt% of acyl chloride solution for 1-3 min; taking out, performing heat treatment for 2min by using 95-degree deionized water, respectively washing for 2min and 0.5min by using 200ppm of sodium hypochlorite aqueous solution and 1000ppm of sodium bisulfite aqueous solution, taking out, and performing heat treatment for 2min by using 95-degree deionized water to obtain the composite film.
The technical effect of the present invention will be further explained with reference to the following non-limiting examples. It is to be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any manner. Unless otherwise indicated, the data described in this section of this specification is measured/calculated using the following parameters:
in the evaluation of the porous separation membrane, pure water flux (L m) was used-2h-1bar-1) Evaluating the performance of the porous separation membrane; in the evaluation of the composite membrane performance, the water flux (L m)-2h-1) The water permeability, reverse salt flux of the composite membrane was evaluated (g m)-2h-1) The salt rejection performance of the composite membrane was evaluated.
Example 1
The preparation method of the porous separation membrane comprises the following specific steps:
(1) 9.6g Mg (NO)3)2·6H2O and 4.7g Al (NO)3)3·9H2O was added to 50ml of pure water to prepare a salt solution, which was added dropwise to 2.12g of NaNO3Adding 50ml of water solution prepared by pure water, controlling the pH value to be 10 by using 3.4M NaOH, stirring for 1h, transferring into a reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12h to obtain MgAl-NO3Hydrotalcite-like compounds. Then, the solution was washed with pure water to pH 7, washed 3 times with acetone, and dried at 100 degrees for use.
The prepared MgAl-NO is mixed3Adding hydrotalcite-like compound into N-methylpyrrolidone solvent, and stirring to obtain the final product with concentration of 1,2,4, 6g L-1The turbidity of the hydrotalcite-like release agent (2) is shown in FIG. 1.
(2) Adding hydrophilic sulfonated polysulfone (sPSf) into an N-methylpyrrolidone solvent, stirring and dissolving, and then adding polysulfone (PSf) to obtain the polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Wherein the sulfonated polysulfone accounts for 0 wt%, 5 wt%, 10 wt% and 15 wt% of the total polymer, i.e. PSf, PSf/sPSf5、PSf/sPSf10And PSf/sPSf15. Then a scraper with the diameter of 150 mu m is used for scraping a film on the non-woven fabric, and the non-woven fabric is immediately immersed in a gel bath (deionized water) for 12 hours after being scraped, so that PSf/sPSf is obtainedx(x-5, 10,15) a porous separation membrane.
(3) A porous separation membrane of a hydrophilic polymer fixed by hydrotalcite-like nano-sheets. Adding 5 wt% of sulfonated polysulfone (sPSf) into hydrotalcite-like compound stripping liquid with different concentrations, stirring and dissolving, and then adding polysulfone (PSf) to obtain the hydrotalcite-like compound nanosheet/polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Then a scraper with the diameter of 150 mu m is used for scraping a film on the non-woven fabric, and the non-woven fabric is immediately immersed in a gel bath (deionized water) for 12 hours after being scraped, so that PSf/sPSf is obtained5-LDHx(x is 1,2,4,6) porous separation membrane, x corresponding to the concentration of hydrotalcite-like release fluid. In addition, in order to explain the effect of the hydrotalcite-like compound having the hydrophilic polymer immobilized thereon, the turbidity of the gel bath was compared, as shown in FIG. 2. In addition, uv-vis spectroscopy characterization (fig. 3) also demonstrated that as the amount of stripping solution increased, the precipitated sulfonated polysulfone decreased.
The performance of the prepared porous separation membrane was evaluated at 25 ℃. The measuring method comprises the following steps: the pressure is tested to be 1bar by adopting a cross-flow filtration mode and taking deionized water as a raw material liquid. The performance of the prepared porous separation membrane is shown in fig. 4.
The results of the comparative test groups, with the same preparation process parameters and test conditions, include:
(1) the pure water flux of PSf of the porous separation membrane without adding the hydrophilic sPSf was 96.7L m-2h-1bar-1。
(2) Porous separation membrane PSf/sPSf added with 5 wt% of hydrophilic sPSf5Has a pure water flux of 146.3L m-2h- 1bar-1(ii) a Porous separation membrane PSf/sPSf added with 10 wt% of hydrophilic sPSf10Has a pure water flux of 181.6L m-2h-1bar-1(ii) a Porous separation membrane PSf/sPSf added with 15 wt% of hydrophilic sPSf15Has a pure water flux of 226.5L m-2h-1bar-1。
(3) Porous separation membrane PSf/sPSf at 5 wt% sPSf5Based on (2), adding 4g L-1After the hydrotalcite-like compound stripping solution (accounting for 0.34 wt% of the total amount of the membrane casting solution) is fixed, the porous separation membrane PSf/sPSf5-LDH4Has a pure water flux of 212.8L m-2h-1bar-1Higher than PSf/sPSf5And PSf/sPSf10A porous separation membrane.
Example 2
The preparation method of the composite membrane comprises the following specific steps:
(1) 9.6g Mg (NO)3)2·6H2O and 4.7g Al (NO)3)3·9H2O was added to 50ml of pure water to prepare a salt solution, which was added dropwise to 2.12g of NaNO3Adding 50ml of water solution prepared by pure water, controlling the pH value to be 10 by using 3.4M NaOH, stirring for 1h, transferring into a reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12h to obtain MgAl-NO3Hydrotalcite-like compounds. Then, the solution was washed with pure water to pH 7, washed 3 times with acetone, and dried at 100 degrees for use. A certain amount of MgAl-NO is added3Adding hydrotalcite-like compound into N-methylpyrrolidone solvent, and stirring to obtain a mixture with certain concentration (1, 2,4 and 6g L)-1) The hydrotalcite-like compound stripping solution of (1).
(2) Adding hydrophilic sulfonated polysulfone (sPSf) into an N-methylpyrrolidone solvent, stirring and dissolving, and then adding polysulfone (PSf) to obtain the polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Wherein the sulfonated polysulfone accounts for 0 wt%, 5 wt%, 10 wt% and 15 wt% of the total polymer, i.e. PSf, PSf/sPSf5、PSf/sPSf10And PSf/sPSf15. Then, the nonwoven fabric was scraped with a 150 μm doctor bladeImmediately immersing into gel bath (deionized water) for 12h after scraping to obtain PSf/sPSfx(x-5, 10,15) a porous separation membrane.
(3) A porous separation membrane of a hydrophilic polymer fixed by hydrotalcite-like nano-sheets. Adding 5 wt% of sulfonated polysulfone (sPSf) into hydrotalcite-like compound stripping liquid with different concentrations, stirring and dissolving, and then adding polysulfone (PSf) to obtain the hydrotalcite-like compound nanosheet/polysulfone/sulfonated polysulfone membrane casting solution with the total polymer amount of 12 wt%. Then a scraper with the diameter of 150 mu m is used for scraping a film on the non-woven fabric, and the non-woven fabric is immediately immersed in a gel bath (deionized water) for 12 hours after being scraped, so that PSf/sPSf is obtained5-LDHx(x is 1,2,4,6) porous separation membrane, x corresponding to the concentration of hydrotalcite-like release fluid.
(4) And (2) putting the compact side of the prepared porous separation membrane into a 3.4 wt% m-phenylenediamine aqueous solution for 2min, taking out, blowing off redundant solution droplets on the surface by using an air knife, putting the compact side into a 0.15 wt% 1,3, 5-benzene tricarboxychloride Isopar-G organic solution for 1min, taking out, performing heat treatment on the compact side for 2min by using 95-degree deionized water, soaking the compact side in 200ppm sodium hypochlorite aqueous solution and 1000ppm sodium bisulfite aqueous solution for 2min and 0.5min respectively, taking out, and performing heat treatment on the compact side for 2min by using 95-degree deionized water to obtain a Polyamide (PA) active layer, namely the composite membrane.
The performance of the prepared composite membrane was evaluated at 25 ℃. The measuring method comprises the following steps: by adopting a cross-flow filtration mode, deionized water is taken as raw material liquid, 1mol/L sodium chloride is taken as driving liquid, the interception layer of the membrane faces to one side of the driving liquid, and the porous supporting layer faces to the side of the raw material liquid, and the performance of the prepared composite membrane is shown in figure 5.
The results of the comparative test groups, with the same preparation process parameters and test conditions, include:
(1) the water flux of the composite membrane PA @ PSf without adding the hydrophilic sPSf is 18.2L m-2h-1Reverse salt flux of 5.1g m-2h-1。
(2) Composite membrane PA @ PSf/sPSf added with 5 wt% of hydrophilic sPSf5Has a water flux of 35.7L m-2h-1Reverse salt flux of 7.3g m-2h-1(ii) a Composite membrane PA @ PSf/sPSf added with 10 wt% of hydrophilic sPSf10Has a water flux of 40.1Lm-2h-1Reverse salt flux of 8.7g m-2h-1(ii) a 15 wt% of hydrophilic sPSf composite membrane PA @ PSf/sPSf is added15Has a water flux of 48.4L m-2h-1Reverse salt flux of 9.3g m-2h-1。
(3) Porous separation membrane PSf/sPSf at 5 wt% sPSf5Based on (2), adding 4g L-1After being fixed, the hydrotalcite-like compound stripping liquid (0.34 wt% of the total amount of the casting solution) is subjected to interfacial polymerization reaction to obtain a composite membrane PA @ PSf/sPSf5-LDH4Has a water flux of 51.7L m-2h-1Higher than PA @ PSf/sPSf5、PA@PSf/sPSf10And PA @ PSf/sPSf15The water flux of (a); reverse salt flux of 9.5g m-2h-1。
The foregoing is illustrative and explanatory only, and it is intended that the present invention be covered by the appended claims, as well as the appended claims, which are appended or substituted in their equivalents.
Claims (10)
1. A preparation method of a hydrotalcite-like nano-sheet modified separation membrane comprises the step of coating and converting a casting solution, and is characterized in that: the casting solution contains hydrotalcite-like nano-sheets.
2. The method according to claim 1, wherein the content of the hydrotalcite-like nanosheets in the casting solution is 0.1-1% by mass.
3. The method according to claim 2, characterized in that the casting solution containing hydrotalcite-like nanosheets is obtained by adding a hydrotalcite-like exfoliating solution to the casting solution; the hydrotalcite-like compound is selected from hydrotalcite-like compounds with nitrate radical, acetate radical, lactate radical and stearate radical intercalation; the organic solvent is selected from one or a mixture of more of formamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone.
4. The method of claim 3, wherein the hydrotalcite-like compound is selected from nitrate intercalated magnesium aluminum hydrotalcite-like compounds.
5. The method according to claim 2, wherein the hydrotalcite-like nanosheets are prepared by mechanically exfoliating hydrotalcite-like nanosheets in an organic solvent, and the concentration of the hydrotalcite-like nanosheets in the obtained hydrotalcite-like nanosheet-containing organic solvent system (hydrotalcite-like exfoliated liquid) is 1 to 10g L-1。
6. The method according to claim 2, wherein the membrane casting solution further comprises a hydrophilic polymer selected from the group consisting of polysulfone, polyethersulfone, polyphenylenesulfone, polyvinylidene fluoride, polybenzimidazole, sulfonated polysulfone, sulfonated polyethersulfone, sulfonated polyetheretherketone, and mixtures thereof.
7. The method of claim 6, wherein the hydrophilic polymer is selected from the group consisting of sulfonated polysulfone, sulfonated polyethersulfone, and sulfonated polyetheretherketone.
8. The method according to claim 1, wherein the solvent (which is an organic solvent) of the casting solution is selected from the group consisting of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and tetrahydrofuran.
9. A hydrotalcite-like nanosheet modified separation membrane prepared by the method of claim 1.
10. A composite membrane, characterized in that it is prepared by interfacial polymerization reaction on the basis of the hydrotalcite-like nanosheet modified separation membrane of claim 5.
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| CN112495199A (en) * | 2020-11-05 | 2021-03-16 | 大连理工大学 | Preparation method of gas separation composite membrane with high-hydrotalcite-content skin layer |
| CN112755814A (en) * | 2020-12-31 | 2021-05-07 | 浙江工业大学 | Black talc nanoparticle modified polyamide composite nanofiltration membrane |
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| CN112755814A (en) * | 2020-12-31 | 2021-05-07 | 浙江工业大学 | Black talc nanoparticle modified polyamide composite nanofiltration membrane |
| CN112844063A (en) * | 2020-12-31 | 2021-05-28 | 浙江工业大学 | Ultrafiltration membrane constructed by high-flux black talc nanosheets and preparation method thereof |
| CN112844063B (en) * | 2020-12-31 | 2022-05-24 | 浙江工业大学 | Ultrafiltration membrane constructed by high-flux black talc nanosheets and preparation method thereof |
| CN112755814B (en) * | 2020-12-31 | 2022-05-24 | 浙江工业大学 | Black talc nanoparticle modified polyamide composite nanofiltration membrane |
| CN113304625A (en) * | 2021-05-28 | 2021-08-27 | 南方科技大学 | Separation membrane, preparation method thereof, membrane separation equipment and sewage treatment method |
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