CN112047427B - Oil-water separation membrane with ion responsiveness, and preparation method and application thereof - Google Patents
Oil-water separation membrane with ion responsiveness, and preparation method and application thereof Download PDFInfo
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- CN112047427B CN112047427B CN201910486261.1A CN201910486261A CN112047427B CN 112047427 B CN112047427 B CN 112047427B CN 201910486261 A CN201910486261 A CN 201910486261A CN 112047427 B CN112047427 B CN 112047427B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an oil-water separation membrane with ion responsiveness, and a preparation method and application thereof. The oil-water separation membrane comprises a polymer porous membrane and zwitter-ion nanogel particles grafted on the polymer porous membrane, wherein the nanogel particles are mainly formed by carrying out reverse microemulsion polymerization on zwitter-ion monomers. The oil-water separation membrane provided by the invention can separate an emulsified oil-water mixture with high flux, high separation efficiency and high pollution resistance, has super strong ion responsiveness, is simple in preparation method, low in energy consumption and cost when being applied to separation of emulsified oil and water, can efficiently realize recycling of oil and water, and has high application value in the aspect of industrial oily wastewater.
Description
Technical Field
The invention relates to an oil-water separation membrane and a preparation method thereof, in particular to an oil-water separation membrane with high flux, pollution resistance and ion responsiveness, a preparation method thereof and application in the field of industrial oily wastewater, and belongs to the field of material science.
Background
The industrial oily wastewater is a complex system containing oil stains, surfactants and other components, and the direct discharge of the industrial oily wastewater can cause great damage to the ecological environment, and the traditional treatment method comprises the following steps: flocculation flotation, adsorption, oxidation, biodegradation and the like, but the efficiency of the methods is low. In contrast, membrane technology has higher efficiency and does not cause secondary pollution. The traditional polymer porous membrane can separate oil-water mixture, has higher flux and low operation pressure, and has great application prospect in the aspect of sewage treatment; however, the flux of the traditional polymer porous membrane can not meet the requirement, and the pollution resistance is poor, so that the flux is limited in practical industrial application.
Disclosure of Invention
The invention mainly aims to provide an oil-water separation membrane with ion responsiveness, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an oil-water separation membrane with ion responsiveness, which comprises a polymer porous membrane and nanogel particles grafted on the polymer porous membrane, wherein the nanogel particles are mainly formed by carrying out reverse microemulsion polymerization on a zwitterionic monomer.
In some embodiments, the polymeric porous membrane is formed primarily from a casting solution comprising a polymeric polymer, a carboxyl-containing additive, and an organic solvent, prepared by a non-solvent phase inversion method.
In some embodiments, the nanogel particles are formed primarily from a reverse microemulsion polymerization reaction of a zwitterionic monomer, an allylamine monomer, and a crosslinker.
The embodiment of the invention also provides a preparation method of the oil-water separation membrane with ion responsiveness, which comprises the following steps: providing a polymer porous membrane and nanogel particles, and grafting the nanogel particles to the polymer porous membrane to form an oil-water separation membrane; wherein, the nanometer gel particles are mainly formed by inverse microemulsion polymerization reaction of zwitterionic monomers.
In some embodiments, the method of making can comprise:
mixing a high molecular polymer, a carboxyl-containing additive and an organic solution to form a membrane casting solution;
and preparing the membrane casting solution into a high-molecular porous membrane by a non-solvent phase conversion method.
In some embodiments, the method of making may comprise:
dissolving a zwitterionic monomer, an allylamine monomer and a cross-linking agent in water to prepare a monomer aqueous solution;
adding an organic solvent which is not soluble with water into the monomer aqueous solution to prepare a reverse microemulsion, and then carrying out polymerization reaction to obtain the nanogel particles.
The embodiment of the invention also provides application of the oil-water separation membrane with the ion responsiveness, such as application in oil-water separation.
For example, an embodiment of the present invention further provides an oil-water separation method, including: and passing a liquid phase system containing oil and water through the ion-responsive oil-water separation membrane to separate oil from water in the liquid phase system.
Preferably, the liquid phase system is an emulsified oil-water mixture.
Preferably, the oil-water separation method further includes: adding a soluble inorganic salt into the liquid phase system.
Compared with the prior art, the invention has the advantages that:
1) According to the invention, the amphiphilic nano-gel particles are modified on the polymer porous membrane as the substrate, so that the super-hydrophilic underwater super-oleophobic oil-water separation membrane is obtained, and the separation performance of the oil-water mixture is obviously improved;
2) The oil-water separation membrane provided by the invention can separate the emulsified oil-water mixture with high flux, high separation efficiency and high pollution resistance, for example, the separation flux of the oil-water separation membrane for 5000ppm emulsified oil-water mixture is 2000Lm -2 h -1 bar -1 The above results show that the flux recovery rate is 95% or more, the separation efficiency is 98% or more, and that in particular, mgCl is present in the presence of inorganic ions, for example, at a concentration of 0.01mol/L 2 When existing, the ion response coefficient is more than 70 times.
3) The preparation method of the oil-water separation membrane provided by the invention is simple, the energy consumption and the cost are low when the membrane is applied to the separation of emulsified oil and water, the reuse of oil and water can be efficiently realized, and the membrane has a very high application value in the aspect of industrial oily wastewater.
Drawings
Fig. 1a and 1b are SEM images of a polymer porous membrane as a base before and after modification with nanogel particles in example 1 of the present invention, respectively, and the inset in fig. 1b is an EDX image of sulfur element (S).
FIG. 2 is a graph showing the ion response of the oil-water separation membrane obtained in example 1 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has found unexpectedly in long-term research and a great deal of practice that the amphiphilic ion nanogel particles are modified on the surface of the polymer porous membrane, so that the hydrophilic underwater oleophobic property of the oil-water separation membrane can be effectively improved, the separation flux, the separation efficiency and the high contamination resistance of the oil-water separation membrane can be further remarkably improved, and particularly, the high-flux and high-efficiency separation of an emulsified oil-water mixed solution can be realized. Based on this finding, the present inventors have proposed a technical solution of the present invention, which will be described in detail below.
One aspect of the embodiment of the invention provides an oil-water separation membrane with ion responsiveness, which comprises a high polymer porous membrane and zwitterionic nanogel particles grafted on the high polymer porous membrane, wherein the nanogel particles are mainly formed by reverse microemulsion polymerization reaction of zwitterionic monomers.
In some embodiments, the porous polymer membrane has pores with a diameter of 50 to 500 nm.
In some embodiments, the nanogel particles have a particle size of 20 to 100 nanometers.
In some embodiments, the polymeric porous membrane is formed primarily from a casting solution comprising a polymeric polymer, a carboxyl-containing additive, and an organic solvent, prepared by a non-solvent phase inversion method.
Further, the high molecular polymer includes, but is not limited to, polyvinylidene fluoride (PVDF), polyacrylic acid-g-polyvinylidene fluoride (PAA-g-PVDF), polyethersulfone (PES), polyacrylonitrile (PAN), polycarbonate (PC), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET).
Further, the additive is selected from carboxyl group-containing compounds capable of being dispersed or dissolved in the casting solution, for example, the additive includes, but is not limited to, a combination of any one or more of ethylenediaminetetraacetic acid (EDTA), citric acid, polyacrylic acid (PAA), polymethacrylic acid, and the like.
In some embodiments, the nanogel particles are formed primarily from a reverse microemulsion polymerization reaction of a zwitterionic monomer, an allylamine monomer, and a crosslinker.
Further, the zwitterionic monomer includes, but is not limited to, any one or a combination of more than two of sulfonate betaine monomers, phosphate betaine monomers and carboxylate betaine monomers.
Further, the crosslinking agent comprises N, N-methylene bisacrylamide.
Another aspect of the embodiments of the present invention provides a method for preparing an oil-water separation membrane with ion responsiveness, including: providing a polymer porous membrane and amphoteric ion nanogel particles, and grafting the nanogel particles to the polymer porous membrane to form an oil-water separation membrane; wherein, the nanometer gel particles are mainly formed by inverse microemulsion polymerization reaction of zwitterionic monomers.
In some embodiments, the method of making may comprise:
mixing a high molecular polymer, a carboxyl-containing additive and an organic solution to form a membrane casting solution;
and preparing the membrane casting solution into a high-molecular porous membrane by a non-solvent phase conversion method.
Further, the concentration of the high molecular polymer in the casting solution is preferably 5 to 20wt%.
Further, the additive is used in an amount of 5 to 25wt% based on the mass of the polymer.
In some more specific embodiments, the preparation method may comprise: preparing the casting solution into a liquid film, and placing the liquid film in a phase inversion solution for 20-120min to obtain the polymer porous membrane, wherein the volume ratio of ethanol to water in the phase inversion solution is 1.
Furthermore, the aperture of the hole contained in the polymer porous membrane is 50-500 nanometers.
In some embodiments, the method of making can comprise:
mixing the components in a molar ratio of 50-90:5-45:5-10 of zwitterionic monomer, allylamine monomer and cross-linking agent are dissolved in water to prepare monomer aqueous solution;
adding an organic solvent which is not soluble with water into the monomer aqueous solution to prepare reversed-phase microemulsion, and then carrying out polymerization reaction at the temperature of 40-60 ℃ for 5-24h to obtain the nanogel particles.
Further, the concentration of the aqueous monomer solution is preferably 0.1g/mL to 0.3g/mL, and particularly preferably 0.1g/mL.
Further, the volume concentration of the inverse microemulsion is preferably 1.
Further, the organic solvent immiscible with water includes, but is not limited to, any one or a combination of two or more of n-hexane, n-heptane, isooctane and cyclohexane.
Furthermore, the particle diameter of the nanogel particles is 20 to 100 nanometers.
In some embodiments, the method of making may comprise:
and immersing the polymer porous membrane into an activator solution for reaction for 1-3h, then cleaning, and immersing into the dispersion liquid of the nanogel particles for 12-36h to obtain the oil-water separation membrane.
Further, the activator solution may be selected from, but not limited to, an EDC/NHS MES buffer solution, etc.
Further, the concentration of the dispersion liquid of the nanogel particles is 5g/L to 15g/L, preferably 5g/L.
Further, the solvent used in the dispersion may be selected from PBS buffer solution and the like, but is not limited thereto.
In some more specific embodiments, the preparation method may comprise:
dissolving a zwitterionic monomer, an allylamine monomer and a cross-linking agent MBAA in water to prepare an aqueous solution, wherein the concentration of the zwitterionic monomer is 0.1g/mL-0.3g/mL; then pouring the mixture into an organic solvent which is not soluble with water, and ultrasonically stirring the mixture to prepare an inverse microemulsion, wherein the volume concentration is 1;
initiating a zwitterionic monomer to perform free radical polymerization reaction at the temperature of 40 +/-3 ℃, continuing the reaction for about 24 hours, centrifuging to obtain nano gel particles, and adding the nano gel particles into a PBS buffer solution to prepare a dispersion solution with the concentration of 5-15 g/L;
adding a high-molecular polymer and a carboxyl-containing additive into an organic solvent to prepare a membrane casting solution, wherein the concentration of the membrane casting solution is about 3g/20mL, and obtaining a high-molecular porous membrane by a non-solvent phase conversion method;
immersing the polymer porous membrane into MES buffer solution of EDC/NHS for 1-3h, rinsing with water for 3 times, and immersing into PBS buffer solution of the obtained nanogel particles for 12-36h to obtain the oil-water separation membrane.
In some more specific embodiments, the method of making can specifically include:
dissolving a zwitterionic monomer, an allylamine monomer and a cross-linking agent MBAA in water to prepare an aqueous solution; then pouring the mixture, tween 80 and span 80 into an organic solvent which is not soluble with water, and ultrasonically stirring for 0.5h to prepare reverse microemulsion;
placing the reverse microemulsion in a three-neck flask at the temperature of 40 +/-3 ℃, introducing nitrogen, adding an initiator AIBN to initiate a zwitterionic monomer to perform free radical polymerization reaction for 24 hours, stopping the reaction, centrifuging to obtain nano gel particles, and dispersing the obtained nano gel particles in a PBS buffer solution to prepare a dispersion solution of the nano gel particles;
adding a high molecular polymer and a carboxyl-containing additive into an organic solvent, and heating for 48 hours at 80 ℃ to prepare a casting solution, wherein the concentration of the casting solution is 3g/20mL; scraping a liquid film on a clean and flat glass plate, and placing the glass plate in ethanol: water =1, in phase-conversion solution for 20min to obtain a polymer porous membrane, rinsing with deionized water for three times, and storing in deionized water;
and (2) immersing the polymer porous membrane into an MES buffer solution of EDC/NHS for 1-3h, rinsing with deionized water for 3 times, immersing into a dispersion solution of the nanogel particles for 12-36h, taking out the deionized water, and rinsing for three times to obtain the oil-water separation membrane which can be placed in the deionized water for storage.
Another aspect of the embodiments of the present invention also provides an oil-water separation membrane having ion responsiveness, which is prepared by any one of the methods described above.
Another aspect of the embodiments of the present invention provides an oil-water separation method, including: and passing a liquid phase system containing oil and water through the ion-responsive oil-water separation membrane to separate oil from water in the liquid phase system.
Further, the liquid phase system is industrial oily wastewater, in particular an emulsified oil-water mixture.
In some preferred embodiments, the preparation method may further include: adding a soluble inorganic salt into the liquid phase system.
Wherein, when the adding concentration of the soluble inorganic salt is 0.1-1mol/L, the oil-water separation membrane has the best effect when separating the emulsified oil-water mixture.
In some more specific embodiments of the present invention, a method of separating an emulsified oil-water mixture may comprise:
providing the oil-water separation membrane;
and (3) enabling the emulsified oil-water mixture to pass through the oil-water separation membrane to realize the separation of oil and water.
Adding MgCl into emulsified oil-water mixture 2 Inorganic salts, mgCl 2 The concentration is about 0.01mol/L, and then the emulsified oil-water mixture containing inorganic salt passes through an oil-water separation membrane to realize the separation of oil and water.
The oil-water separation membrane provided by the invention is a super-hydrophilic underwater super-oleophobic separation membrane, can realize oil-water separation with high flux, high separation efficiency and high pollution resistance, particularly shows excellent separation performance on emulsified oil-water mixtures, has super strong ion responsiveness, is low in oil-water separation cost, can realize reuse of oil and water, and has wide application prospects in the fields of industrial wastewater treatment and the like.
The technical solution of the present invention is explained in more detail below with reference to several preferred embodiments. The specific examples set forth below are intended only to further illustrate and explain the present invention and are not intended to be limiting.
For better illustration and explanation of the present invention, the preparation of the amphiphilic ionic nanogel and the example of the salt ion-responsive oil-water separation membrane are separately illustrated.
Preparation of amphiphilic ionic nanogels
Example 1 the amphiphilic ionic nanogel of this example can be prepared by the following procedure:
50 parts (all molar parts, unless otherwise specified below) of a sulfonate betaine monomer, 45 parts of an allylamine monomer, and 5 parts of a crosslinking agent MBAA were dissolved in deionized water to obtain a monomer solution having a concentration of 0.1g/mL. Adding the monomer solution into n-hexane, and ultrasonically stirring for 0.5h to prepare the reverse microemulsion with the volume ratio of 1. Initiating the monomer to perform free radical polymerization reaction for 24 hours at the temperature of 40 ℃, stopping the reaction, and centrifuging to obtain the zwitterion nanogel particles with the evaluation particle size of about 100 nanometers.
Example 2 the amphiphilic ionic nanogel of this example can be prepared by the following procedure:
90 parts of a sulfonate betaine monomer, 5 parts of an allylamine monomer and 5 parts of a crosslinking agent MBAA are dissolved in deionized water to obtain a monomer solution with a concentration of 0.1g/mL. Adding the monomer solution into n-hexane, and ultrasonically stirring for 0.5h to prepare the reverse microemulsion with the volume ratio of 1. Initiating the monomer to perform free radical polymerization reaction for 24 hours at the temperature of 40 ℃, stopping the reaction, and centrifuging to obtain the zwitterion nanogel particles with the evaluation particle size of about 50 nanometers.
Example 3 the amphiphilic ionic nanogel of this example can be prepared by the following procedure:
50 parts of a sulfonate betaine monomer, 45 parts of an allylamine monomer and 5 parts of a crosslinking agent MBAA are dissolved in deionized water to obtain a monomer solution with the concentration of 0.1g/mL. Adding the monomer solution into n-hexane, and ultrasonically stirring for 0.5h to prepare the reverse microemulsion with the volume ratio of 1. Initiating the monomer to perform free radical polymerization reaction for 24 hours at the temperature of 40 ℃, stopping the reaction, and centrifuging to obtain the zwitterion nanogel particles with the evaluation particle size of about 20 nanometers.
Example 4 the amphiphilic ionic nanogel of this example can be prepared by the following procedure:
75 parts of sulfonate betaine monomer, 15 parts of allylamine monomer and 10 parts of crosslinking agent MBAA are dissolved in deionized water to obtain a monomer solution with the concentration of 0.1g/mL. Adding the monomer solution into n-hexane, and ultrasonically stirring for 0.5h to prepare the reverse microemulsion with the volume ratio of 1. Initiating the monomer to perform free radical polymerization reaction for 24 hours at the temperature of 40 ℃, stopping the reaction, and centrifuging to obtain the zwitterion nanogel particles with the evaluation particle size of about 50 nanometers.
Examples of salt ion-responsive oil-water separation membranes
Example 5
The oil-water separation membrane of the present example can be prepared by the following process:
adding PVDF powder and ethylene diamine tetraacetic acid into N, N-Dimethylformamide (DMF), heating and stirring at 80 ℃ for 48h for dissolving, wherein the concentration of the PVDF powder is 10wt%, and the addition amount of the ethylene diamine tetraacetic acid is 25wt% of the mass of the PVDF; coating the obtained casting solution on a glass substrate, and then immersing the glass substrate into a phase inversion solution consisting of ethanol and water for phase inversion for 40min to obtain a high-molecular porous membrane with the average pore diameter of 200nm, wherein the volume ratio of ethanol to water in the phase inversion solution is 1 (v: v); the obtained polymer porous membrane is immersed into a MES solution of EDC/NHS for activation for 1h, rinsed for three times, and then placed in the nano gel particle dispersion liquid obtained in the example 1 for reaction for 12h. After the reaction, an oil-water separation membrane is obtained, taken out, rinsed for three times by deionized water and stored in the deionized water.
Through tests, the oil-water separation membrane prepared in the embodiment has the flux of 28.5Lm for 5000ppm n-hexane/Tween 80/water emulsion under the conditions of the test temperature of 25 ℃, the operation pressure of 1bar and the deionized water -2 h -1 bar -1 The recovery rate of the flux is 97.6 percent, the retention rate is 99.2 percent, and the flux of 5000ppm soybean oil/Tween 80/water emulsion is 28Lm -2 h -1 bar -1 The flux recovery rate is 96.4 percent, and the retention rate is 99.7 percent; at 0.01mol/LMgCl 2 Under the condition of ion concentration, the flux of the emulsion of 5000ppm n-hexane/Tween 80/water is 2310Lm -2 h - 1 bar -1 The flux recovery rate is 98.2 percent, the retention rate is 98.2 percent, and the flux to 5000ppm soybean oil/Tween 80/water emulsion is 2280Lm -2 h -1 bar -1 The flux recovery rate is 97.2 percent, and the retention rate is 98.7 percent;
FIGS. 1a to 1b show SEM images of the surface of the polymer porous membrane before and after the nanogel particles are grafted in this example, respectively. As can be seen from FIG. 1b, the nanogel particles are uniformly grafted on the PVDF polymer porous membrane substrate, and the surface structure of the polymer porous membrane is not obviously changed. FIG. 2 shows the MgCl pair of the oil-water separation membrane obtained in this example 2 As shown in a solution ionic response data chart, the ionic response coefficient of the oil-water separation membrane can reach 80 times when the concentration of magnesium ions is 0.01 mol/L.
Example 6
The oil-water separation membrane of the present example can be prepared by the following process:
adding PVDF powder and ethylenediamine tetraacetic acid into N, N-Dimethylformamide (DMF), heating and stirring at 80 ℃ for 48h for dissolving, wherein the concentration of the PVDF powder is 5wt%, and the addition amount of the ethylenediamine tetraacetic acid is 10wt% of the PVDF; coating the casting solution on a glass substrate, and then immersing the glass substrate into a phase inversion solution consisting of ethanol and water for phase inversion for 20min to obtain a high-molecular porous membrane with the average pore diameter of 500nm, wherein the volume ratio of the ethanol to the water in the phase inversion solution is 2 (v: v); the obtained polymer porous membrane is immersed in MES solution of EDC/NHS for activation for 1h, rinsed for three times, and then placed in the nano gel particle dispersion liquid obtained in the example 2 for reaction for 12h. And obtaining an oil-water separation membrane after reaction, taking out the oil-water separation membrane, rinsing the oil-water separation membrane for three times by using deionized water, and storing the oil-water separation membrane in the deionized water.
Example 7
The oil-water separation membrane of the present example can be prepared by the following process:
adding PVDF powder and ethylene diamine tetraacetic acid into N, N-Dimethylformamide (DMF), heating and stirring at 80 ℃ for 48h for dissolving, wherein the concentration of the PVDF powder is 20wt%, and the addition amount of the ethylene diamine tetraacetic acid is 5wt% of the mass of the PVDF; coating the casting solution on a glass substrate, and then immersing the glass substrate into a phase inversion solution consisting of ethanol and water for phase inversion for 20min to obtain a high-molecular porous membrane with the average pore diameter of 50nm, wherein the volume ratio of ethanol to water in the phase inversion solution is 1; the obtained polymer porous membrane is immersed in MES solution of EDC/NHS for activation for 3h, rinsed for three times, and then placed in the nano gel particle dispersion liquid obtained in the example 3 for reaction for 36h. After the reaction, an oil-water separation membrane is obtained, taken out, rinsed for three times by deionized water and stored in the deionized water.
Example 8
Adding PES powder and polyacrylic acid (PAA) into N, N-Dimethylformamide (DMF), heating and stirring at 80 ℃ for 48h for dissolving, wherein the concentration of the PES powder is 12wt%, and the addition amount of the polyacrylic acid (PAA) is 8wt% of the mass of the PES powder; coating the obtained casting solution on a glass substrate, and then soaking the glass substrate into a phase inversion solution consisting of ethanol and water for phase inversion for 40min, wherein the volume ratio of the ethanol to the water in the phase inversion solution is 1; the obtained polymer porous membrane is immersed in MES solution of EDC/NHS for 1h, rinsed for three times, and then placed in the nano gel particle dispersion liquid obtained in the example 4 for reaction for 24h. And obtaining an oil-water separation membrane after reaction, taking out the oil-water separation membrane, rinsing the oil-water separation membrane for three times by using deionized water, and storing the oil-water separation membrane in the deionized water.
Through tests, the oil-water separation membrane prepared in the embodiment has the flux of 26.2Lm for 5000ppm n-hexane/Tween 80/water emulsion under the conditions of the test temperature of 25 ℃, the operation pressure of 1bar and the deionized water -2 h -1 bar -1 The flux recovery rate is 96.5 percent, the retention rate is 98.5 percent, and the flux to 5000ppm soybean oil/Tween 80/water emulsion is 26Lm -2 h -1 bar -1 The flux recovery rate is 98.3 percent, and the retention rate is 98.7 percent; at 0.01mol/LMgCl 2 Under the condition of ion concentration, the flux of emulsion of 5000ppm n-hexane/Tween 80/water is 2258Lm -2 h - 1 bar -1 The flux recovery rate is 99.0 percent, the retention rate is 98.2 percent, and the flux to 5000ppm soybean oil/Tween 80/water emulsion is 2237Lm -2 h -1 bar -1 The flux recovery rate was 97.4% and the rejection rate was 98.9%.
It should be noted that all the oil-water separation membranes obtained in the examples were tested by applying a cross flow method.
Wherein the flux is based on the volume of liquid filtered per hour per square meter of membrane area and normalized to unit atmosphere:
the flux recovery rate is calculated according to the ratio of the second separation flux to the first separation flux, and the calculation formula is as follows:
r＝P 2 /P 1
wherein, the retention rate of the oil phase in the oil-water emulsion is calculated according to the ratio of the concentration of the oil phase in the penetrating fluid to the concentration of the oil phase in the feeding fluid, and the calculation formula is as follows:
wherein, the ion response coefficient of the oil-water separation membrane is calculated according to the ratio of the flux at a certain ion concentration to the flux at no ion, and the calculation formula is as follows:
the meaning of each symbol in the above formulas is known to those skilled in the art.
In addition, the inventors have also conducted experiments with other raw materials and conditions and the like listed in the present specification by referring to the manner of examples 1 to 5, and have also produced an oil-water separation membrane having high permeation flux, high efficiency rejection and ultrahigh ion responsiveness to an oil-water emulsion.
It should be understood that the above are only examples of the present invention, and the scope of the present invention should not be limited thereto. All the technical solutions formed by equivalent transformation or equivalent replacement fall within the protection scope of the present invention.
Claims (13)
1. An oil-water separation membrane with ion responsiveness is characterized by comprising a polymer porous membrane and zwitter-ion nanogel particles grafted on the polymer porous membrane; the particle size of the zwitter ion nanogel particles is 20-100 nanometers, and the molar ratio of the zwitter ion nanogel particles to the total volume of the gel particles is 50-90:5-45:5-10 of zwitterion monomer, allylamine monomer and cross-linking agent are prepared by reverse microemulsion polymerization reaction; wherein the zwitterionic monomer is selected from any one or the combination of more than two of sulfonate betaine monomers, phosphate betaine monomers and carboxylate betaine monomers.
2. The oil-water separation membrane according to claim 1, wherein: the pore diameter of the pores in the polymer porous membrane is 50-500 nanometers.
3. The oil-water separation membrane according to claim 1, wherein: the polymer porous membrane is prepared from a casting solution containing a high molecular polymer, a carboxyl-containing additive and an organic solvent by a non-solvent phase inversion method; wherein the high molecular polymer is selected from one or more of polyvinylidene fluoride, polyacrylic acid-g-polyvinylidene fluoride, polyether sulfone, polyacrylonitrile, polycarbonate, polystyrene, polyvinyl chloride and polyethylene terephthalate; the additive is selected from carboxyl-containing compounds capable of being dispersed or dissolved in the casting solution.
4. The oil-water separation membrane according to claim 3, wherein: the additive is selected from one or more of ethylenediamine tetraacetic acid, citric acid, polyacrylic acid and polymethacrylic acid.
5. The oil-water separation membrane according to claim 1, wherein: the cross-linking agent is N, N-methylene bisacrylamide.
6. A preparation method of an oil-water separation membrane with ion responsiveness is characterized by comprising the following steps:
mixing the components in a molar ratio of 50-90:5-45:5-10 of a zwitterionic monomer, an allylamine monomer and a cross-linking agent are dissolved in water to prepare a monomer aqueous solution, wherein the zwitterionic monomer is selected from any one or a combination of more than two of a sulfonate betaine monomer, a phosphate betaine monomer and a carboxylate betaine monomer;
adding an organic solvent which is not soluble with water into the monomer aqueous solution to prepare a reverse microemulsion, and then carrying out polymerization reaction at the temperature of 40-60 ℃ for 5-24h to obtain the zwitterion nanogel particles with the particle size of 20-100 nm;
and immersing the polymer porous membrane into an activator solution for reaction for 1-3h, wherein the reaction temperature is 25-60 ℃, then cleaning, immersing into the dispersion liquid of the nanogel particles for 12-36h, and grafting the nanogel particles to the polymer porous membrane to obtain the oil-water separation membrane.
7. The method according to claim 6, characterized by comprising:
mixing a high-molecular polymer, a carboxyl-containing additive and an organic solution to form a casting solution, wherein the concentration of the high-molecular polymer is 5-20wt%, and the mass of the high-molecular polymer is 5-25wt%, the high-molecular polymer is selected from one or more of polyvinylidene fluoride, polyacrylic acid-g-polyvinylidene fluoride, polyether sulfone, polyacrylonitrile, polycarbonate, polystyrene, polyvinyl chloride and polyethylene terephthalate, and the additive is selected from carboxyl-containing compounds capable of being dispersed or dissolved in the casting solution;
preparing the casting solution into a liquid film, and placing the liquid film in a phase inversion solution for 20-120min to obtain the polymer porous membrane, wherein the volume ratio of ethanol to water in the phase inversion solution is 1.
8. The method of claim 6, wherein: the pore diameter of the holes contained in the polymer porous membrane is 50-500 nanometers.
9. The production method according to claim 6, characterized by comprising: the concentration of the monomer aqueous solution is 0.1g/mL-0.3g/mL;
and/or the volume ratio of the aqueous solution to the organic solvent in the reverse microemulsion is 1-1.
10. The method of claim 6, wherein:
the activating agent solution is MES buffer solution containing EDC and NHS;
the concentration of the dispersion liquid of the nanogel particles is 5g/L-15g/L, wherein the adopted solvent is PBS buffer solution.
11. An oil-water separation membrane having ion-responsiveness prepared by the method according to any one of claims 6 to 10.
12. An oil-water separation method is characterized by comprising the following steps: passing a liquid phase system comprising oil and water through the ion-responsive oil-water separation membrane of any one of claims 1 to 5 and 11, thereby separating oil from water in the liquid phase system;
the liquid phase system is an emulsified oil-water mixture.
13. The oil-water separation method according to claim 12, wherein: the liquid phase system is added with 0.1-1mol/L soluble inorganic salt.
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| CN102294177A (en) * | 2011-08-17 | 2011-12-28 | 浙江大学 | Sulfobetaine type amphion-containing reverse osmosis composite film |
| CN106139937A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | High molecular weight hydrophilic Modified Membrane, its preparation method and application |
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| CN102294177A (en) * | 2011-08-17 | 2011-12-28 | 浙江大学 | Sulfobetaine type amphion-containing reverse osmosis composite film |
| CN106139937A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | High molecular weight hydrophilic Modified Membrane, its preparation method and application |
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